U.S. patent application number 08/946850 was filed with the patent office on 2001-08-16 for ion conductive laminate and production method and use thereof.
Invention is credited to HIRATA, MOTOYUKI, NAIJO, SHUICHI, OHKUBO, TAKASHI, TAKEUCHI, MASATAKA, YOTSUYANAGI, JUNJI.
Application Number | 20010014420 08/946850 |
Document ID | / |
Family ID | 27307358 |
Filed Date | 2001-08-16 |
United States Patent
Application |
20010014420 |
Kind Code |
A1 |
TAKEUCHI, MASATAKA ; et
al. |
August 16, 2001 |
ION CONDUCTIVE LAMINATE AND PRODUCTION METHOD AND USE THEREOF
Abstract
A laminate comprising an ion conductive material having
excellent ion conductivity at room temperature or at lower
temperatures, a small water content, sufficiently high mechanical
strength and storage stability to allow for handling the ion
conductive material in practice, and a form which is easily
integrated into an electrochemical element or electrochemical
devices. Also disclosed is a production method thereof, and a
method of producing a battery, a capacitor or an electrochemical
element or apparatus using the laminate. The laminate comprises an
intermediate layer of an ion conductive material having on the
upper and lower portions thereof outer layers having an ion
conductivity lower than that of the intermediate layer.
Furthermore, at least one of the outer layers is a layer comprising
a non electron-conductive material.
Inventors: |
TAKEUCHI, MASATAKA; (CHIBA,
JP) ; NAIJO, SHUICHI; (CHIBA, JP) ; OHKUBO,
TAKASHI; (CHIBA, JP) ; YOTSUYANAGI, JUNJI;
(CHIBA, JP) ; HIRATA, MOTOYUKI; (KAWASAKI-SHI,
JP) ; HIRATA, MOTOYUKI; (KAWASAKI-SHI, JP) |
Correspondence
Address: |
SUGHRUE MION ZINN MACPEAK AND SEAS
2100 PENNSYLVANIA AVENUE NW
WASHINGTON
DC
200373202
|
Family ID: |
27307358 |
Appl. No.: |
08/946850 |
Filed: |
October 8, 1997 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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08946850 |
Oct 8, 1997 |
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08822465 |
Mar 21, 1997 |
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08946850 |
Oct 8, 1997 |
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PCT/JP97/00944 |
Mar 21, 1997 |
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60014567 |
Apr 1, 1996 |
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Current U.S.
Class: |
429/209 ;
156/272.2; 156/273.3; 428/207; 428/423.7; 428/425.5; 428/425.8;
428/458; 428/474.7; 428/482; 429/188; 429/207 |
Current CPC
Class: |
Y10T 428/31598 20150401;
H01M 8/1093 20130101; B32B 7/025 20190101; Y10T 428/31728 20150401;
G02F 1/1525 20130101; H01G 11/82 20130101; Y10T 428/31565 20150401;
H01G 9/155 20130101; H01G 11/56 20130101; Y10T 428/31681 20150401;
Y02E 60/13 20130101; Y10T 428/30 20150115; G01N 27/4073 20130101;
Y02E 60/50 20130101; H01M 8/1004 20130101; H01M 8/1025 20130101;
H01M 2300/0082 20130101; Y10T 428/31507 20150401; Y10T 428/31605
20150401; Y10T 428/24901 20150115; Y10T 428/31794 20150401; H01G
11/84 20130101; H01M 6/181 20130101; H01M 8/109 20130101; Y10T
428/31765 20150401; B32B 37/24 20130101; H01M 8/1053 20130101; H01M
8/1067 20130101 |
Class at
Publication: |
429/209 ;
428/458; 428/474.7; 428/482; 428/423.7; 428/425.5; 428/425.8;
429/188; 428/207; 429/207; 156/272.2; 156/273.3 |
International
Class: |
B32B 003/00; H01M
010/26 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 21, 1996 |
JP |
8-93682 |
Claims
We claim:
1. A laminate comprising Layer A, Layer B and Layer C, wherein
Layer A is disposed between Layer B and Layer C, Layer A comprises
an ion conductive material, Layer B and Layer C each comprises a
material having an ion conductivity lower than that of Layer A, and
at least one of Layer B and Layer C comprises a non
electron-conductive material.
2. The laminate according to claim 1, wherein at least one of Layer
B and Layer C has a contact angle of 80.degree. or less with
polyethylene glycol having an average molecular weight of about
400.
3. The laminate according to claim 1, wherein at least one of Layer
B and Layer C has a contact angle of 60.degree. or less with
polyethylene glycol having an average molecular weight of about
400.
4. The laminate according to claim 1, wherein Layer B and Layer C
each is a liquid impermeable layer.
5. The laminate according to claim 1, wherein Layer B and Layer C
each is a water impermeable layer.
6. The laminate according to claim 1, wherein at least one of Layer
B and Layer C comprises a material having a dielectric constant of
8 or less.
7. The laminate according to claim 1, wherein at least one of Layer
B and Layer C has an ion conductivity that is one tenth the ion
conductivity of Layer A or less.
8. The laminate according to claim 1, wherein at least one of Layer
B and Layer C comprises a thermoplastic resin or a composition
containing a thermoplastic resin.
9. The laminate according to claim 1, wherein at least one of Layer
B and Layer C comprises an engineering plastic, a thermosetting
resin or a composition containing one of an engineering plastic or
a thermosetting resin.
10. The laminate according to claim 1, wherein the ion conductive
material of Layer A has a specific resistivity of 10.sup.6
.OMEGA..multidot.cm or less.
11. The laminate according to claim 1, wherein the ion conductive
material of Layer A has a specific resistivity of 10.sup.5
.OMEGA..multidot.cm or less.
12. The laminate according to claim 1, wherein Layer A has a
thickness of from 0.1 to 1,000 .mu.m.
13. The laminate according to claim 1, wherein Layer A has a water
content of 200 ppm or less.
14. The laminate according to claim 1, wherein Layer A has a peel
strength such that Layer B or Layer C can be peeled off without
substantially deforming the shape of Layer A.
15. The laminate according to claim 1, wherein at least one of
Layer B and Layer C is a light-transmissible layer.
16. The laminate according to claim 1, wherein none of Layer B and
Layer C are light-transmissible layers.
17. The laminate according to claim 1, wherein both of Layer B and
Layer C are gas impermeable layers.
18. The laminate according to claim 1, wherein Layer B or Layer C
comprises an electron conductive material, and the electron
conductive material-containing layer is connected to an electron
conductive electric conductor.
19. The laminate according to claim 1, further comprising electron
conductive electric conductors connected to two different sites of
Layer A.
20. The laminate according to claim 1, wherein Layer A comprises a
material containing a cross-linked polymer as a constituent
component.
21. The laminate according to claim 1, wherein Layer A comprises a
material containing a cross-linked polymer having at least one
alkyleneoxy-containing chain in the main chain and/or in the side
chain thereof as a constituent component.
22. The laminate according to claim 1, wherein Layer A comprises a
material containing a cross-linked polymer having at least one
alkyleneoxy-containing chain and at least one --NH-- C(.dbd.O)--O--
bond in the main chain and/or in the side chain thereof as a
constituent component.
23. The laminate according to claim 1, wherein Layer A comprises a
material containing, as a constituent component, a polymer of a
(meth)acryloyl-base compound having a structure substituted by at
least one unit represented by formula (1) and/or a copolymer
containing said compound as a copolymer component:
CH.sub.2.dbd.C(R.sup.1)CO[O(CH.sub.2).-
sub.x(CH(CH.sub.3)).sub.y].sub.zNHCOO--R.sup.2-- (1) wherein
R.sup.1 represents hydrogen or an alkyl group, R.sup.2 represents a
divalent organic group containing an oxyalkylene group, said
organic group may have any of linear, branched and cyclic
structures and may contain one or more elements other than carbon,
hydrogen and oxygen, x and y each represents 0 or an integer of
from 1 to 5, z represents 0 or a numerical value of from 1 to 10,
provided that when both of x and y are zero, z is zero; the moiety
(CH.sub.2) and the moiety (CH(CH.sub.3)) maybe randomly configured,
provided that when two or more units represented by formula (1) are
present in the same molecule, R.sup.1 and R.sup.2 of one unit may
be different from R.sup.1 and R.sup.2 of the other units, and the
values x, y and z of one unit may be different from the values x, y
and z of the other units.
24. The laminate according to claim 1, wherein the ion conductive
material of Layer A contains at least one of an electrolyte salt
and a solvent.
25. The laminate according to claim 24, wherein the electrolyte
salt is at least one selected from the group consisting of an
alkali metal salt, a quaternary ammonium salt and a quaternary
phosphonium salt.
26. The laminate according to claim 24, wherein the solvent is at
least one selected from the group consisting of a carbonate-base
compound, a lactone-base compound and an ether-base compound, each
having a dielectric constant of 1 or more.
27. The laminate according to claim 1, further comprising a thin
layer comprising a metal, a metal oxide or carbon which is present
between Layer A and Layer B and/or between Layer A and Layer C.
28. The laminate according to claim 1, further comprising an
electron conductive thin layer which is present between Layer A and
either one of Layer B and Layer C, and the other of Layer B and
Layer C comprises a non electron-conductive material.
29. The laminate according to claim 27 or 28, wherein the thin
layer is connected to an electron conductive electric
conductor.
30. A method for producing a laminate comprising Layer A, Layer B
and Layer C, wherein Layer A is disposed between Layer B and Layer
C, Layer A comprises an ion conductive material, Layer B and Layer
C each comprises a material having an ion conductivity lower than
that of Layer A, and at least one of Layer B and Layer C comprises
a non electron-conductive material, comprising the steps of (i)
laminating Layer A on Layer B in such manner that the material of
Layer A substantially does not flow or move on Layer B, to thereby
provide a laminate structure consisting of Layer B/Layer A, (ii)
laminating Layer C on Layer A to provide a laminate structure
consisting of Layer B/Layer A/Layer C, and (iii) then applying
pressure to the laminate structure with a force applied on the
Layer B side surface and a force in opposition thereto applied on
the Layer C side surface.
31. A method for producing a laminate comprising Layer A, Layer B
and Layer C, wherein Layer A is disposed between Layer B and Layer
C, Layer A comprises an ion conductive material, Layer B and Layer
C each comprises a material having an ion conductivity lower than
that of Layer A, and at least one of Layer B and Layer C comprises
a non electron-conductive material, comprising the steps of (i)
laminating Layer A on Layer B in such manner that the material of
Layer A substantially does not flow or move on Layer B, to thereby
provide a laminate structure consisting of Layer B/Layer A, wherein
Layer A comprises an ion conductive material containing a curable
substance,(ii) laminating Layer C on Layer A to provide a laminate
structure consisting of Layer B/Layer A/Layer C, and (iii) then
applying pressure to the laminate structure with a force applied on
the Layer B side surface and a force in opposition thereto applied
on the Layer C side surface.
32. A method for producing a laminate comprising Layer A, Layer B
and Layer C, wherein Layer A is disposed between Layer B and Layer
C, Layer A comprises an ion conductive material, Layer B and Layer
C each comprises a material having an ion conductivity lower than
that of Layer A, and at least one of Layer B and Layer C comprises
a non electron-conductive material, comprising the steps of (i)
laminating Layer A on Layer B in such manner that the material of
Layer A substantially does not flow or move on Layer B, to provide
a laminate structure consisting of Layer B/Layer A, wherein Layer A
comprises an ion conductive material containing a curable
substance, (ii) heating and/or irradiating the laminate structure
with active light to cure Layer A, (iii) laminating Layer C on
Layer A to provide a laminate structure consisting of Layer B/Layer
A/Layer C, and (iv) then applying pressure to the laminate
structure with a force applied on the Layer B side surface and a
force in opposition thereto applied on the Layer C side
surface.
33. The method for producing a laminate according to any one of
claims 30 to 32, wherein the laminate is heated and/or irradiated
with active light before or during the pressure applying step.
34. The method for producing a laminate according to any one of
claims 30 to 32, wherein the laminate structure consisting of Layer
B/Layer A comprises Layer A substantially in a non-flowable state
as a constituent layer which is obtained by laminating Layer A
comprising an ion conductive material containing a solvent on Layer
B comprising a material having an ion conductivity lower than that
of Layer A in such manner that the material of Layer A
substantially does not flow or move on Layer B and then removing
the solvent.
35. A method for producing a laminate comprising Layer A, Layer B
and Layer C, wherein Layer A is disposed between Layer B and Layer
C, Layer A comprises an ion conductive material, Layer B and Layer
C each comprises a material having an ion conductivity lower than
that of Layer A, and at least one of Layer B and Layer C comprises
a non electron-conductive material, comprising the steps of (i)
forming a thin layer D.sub.1 comprising a metal, a metal oxide or
carbon on one surface of Layer B, (ii) laminating Layer A on the
thin layer D.sub.1, in such manner that the material of Layer A
substantially does not flow or move on the thin layer D.sub.1, to
provide a laminate structure consisting of Layer B/thin layer
D.sub.1/Layer A, (iii) laminating Layer C on Layer A, to provide a
laminate structure consisting of Layer B/thin layer D.sub.1/Layer
A/Layer C, and (iv) then applying pressure to the laminate
structure with a force applied on the Layer B side surface and a
force in opposition thereto applied on the Layer C side
surface.
36. A method for producing a laminate comprising Layer A, Layer B
and Layer C, wherein Layer A is disposed between Layer B and Layer
C, Layer A comprises an ion conductive material, Layer B and Layer
C each comprises a material having an ion conductivity lower than
that of Layer A, and at least one of Layer B and Layer C comprises
a non electron-conductive material, comprising the steps of (i)
forming a thin layer D.sub.2 comprising a metal, a metal oxide or
carbon on one surface of Layer C, (ii) laminating on the thin layer
D.sub.2 the Layer A surface of a laminate structure consisting of
Layer B/Layer A obtained by laminating Layer A on Layer B in such
manner that the material of Layer A substantially does not flow or
move on Layer B, to provide a laminate structure consisting of
Layer C/thin layer D.sub.2/Layer A/Layer B, and (iii) then applying
pressure to the laminate structure with a force applied on the
Layer B side surface and a force in opposition thereto applied on
the Layer C side surface.
37. A method for producing a laminate comprising Layer A, Layer B
and Layer C, wherein Layer A is disposed between Layer B and Layer
C, Layer A comprises an ion conductive material, Layer B and Layer
C each comprises a material having an ion conductivity lower than
that of Layer A, and at least one of Layer B and Layer C comprises
a non electron-conductive material, comprising the steps of (i)
forming a thin layer D.sub.1 comprising a metal, a metal oxide or
carbon on one surface of Layer B, (ii) laminating Layer A on the
thin layer D.sub.1 in such manner that the material of Layer A
substantially does not flow or move on the thin layer D.sub.1, to
provide a laminate structure consisting of Layer B/thin layer
D.sub.1/Layer A, (iii) laminating Layer C on Layer A to provide a
laminate structure consisting of Layer B/thin layer D.sub.1/Layer
A/Layer C, and (iv) then applying pressure to the laminate
structure with a force applied on the Layer B side surface and a
force in opposition thereto applied on the Layer C side surface,
wherein Layer A comprises an ion conductive material containing a
curable substance.
38. A method for producing a laminate comprising Layer A, Layer B
and Layer C, wherein Layer A is disposed between Layer B and Layer
C, Layer A comprises an ion conductive material, Layer B and Layer
C each comprises a material having an ion conductivity lower than
that of Layer A, and at least one of Layer B and Layer C comprises
a non electron-conductive material, comprising the steps of (i)
forming a thin layer D.sub.2 comprising a metal, a metal oxide or
carbon on one surface of Layer C, (ii) laminating on the thin layer
D.sub.2 the Layer A surface of a laminate structure consisting of
Layer B/Layer A obtained by laminating Layer A on Layer B in such
manner that the material of Layer A substantially does not flow or
move on Layer B, to provide a laminate structure consisting of
Layer C/thin layer D.sub.2/Layer A/Layer B, and (iii) then applying
pressure to the laminate structure with a force applied on the
Layer B side surface and a force in opposition thereto applied on
the Layer C side surface, wherein Layer A comprises an ion
conductive material containing a curable substance.
39. A method for producing a laminate comprising Layer A, Layer B
and Layer C, wherein Layer A is disposed between Layer B and Layer
C, Layer A comprises an ion conductive material, Layer B and Layer
C each comprises a material having an ion conductivity lower than
that of Layer A, and at least one of Layer B and Layer C comprises
a non electron-conductive material, comprising the steps of (i)
forming a thin layer D.sub.1 comprising a metal, a metal oxide or
carbon on one surface of Layer B, (ii) laminating Layer A on the
thin layer D.sub.1 in such manner that the material of Layer A
substantially does not flow or move on the thin layer D.sub.1, to
provide a laminate structure consisting of Layer B/thin layer
D.sub.1/Layer A, wherein Layer A comprises an ion conductive
material containing a curable substance, (iii) heating and/or
irradiating the laminate structure with active light to cure Layer
A, (iv) laminating Layer C on Layer A to provide a laminate
structure consisting of Layer B/thin layer D.sub.1/Layer A/Layer C,
and (v) then applying pressure to the laminate structure with a
force applied on the Layer B side surface and a force in opposition
thereto applied on the Layer C side surface.
40. A method for producing a laminate comprising Layer A, Layer B
and Layer C, wherein Layer A is disposed between Layer B and Layer
C, Layer A comprises an ion conductive material, Layer B and Layer
C each comprises a material having an ion conductivity lower than
that of Layer A, and at least one of Layer B and Layer C comprises
a non electron-conductive material, comprising the steps of (i)
laminating Layer A on Layer B in such manner that the material of
Layer A substantially does not flow or move on Layer B, to provide
a laminate structure consisting of Layer B/Layer A, wherein Layer A
comprises an ion conductive material containing a curable
substance, (ii) heating and/or irradiating the laminate structure
with active light to cure Layer A, (iii) laminating the thin layer
D.sub.2 surface of Layer C having on one surface thereof a thin
layer D.sub.2 comprising a metal, a metal oxide or carbon, to
provide a laminate structure consisting of Layer C/thin layer
D.sub.2/Layer A/Layer B, and (iv) then applying pressure to the
laminate structure with a force applied on the Layer B side surface
and a force in opposition thereto applied on the Layer C side
surface.
41. A method for producing an electrochemical element which
comprises the steps of (i) providing a laminate comprising Layer A,
Layer B and Layer C, wherein Layer A is disposed between Layer B
and Layer C, Layer A comprises an ion conductive material, Layer B
and Layer C each comprises a material having an ion conductivity
lower than that of Layer A, and at least one of Layer B and Layer C
comprises a non electron-conductive material, (ii) removing at
least one of Layer B and Layer C from Layer A of the laminate, or
removing Layer B or Layer C having on the surface thereof facing
Layer A a thin layer comprising a metal, a metal oxide or carbon,
together with said thin layer from Layer A of said laminate, and
(iii) forming a layer comprising a material containing an
electrochemically-active substance on at least one removal surface
of Layer A.
42. The method as claimed in claim 41, wherein the electrochemical
element is an electrochemical power generating element, an
electrochemical coloring element, an electrochemical light-emitting
element, a battery, a capacitor, an electrochromic element, a
photoelectric cell or a solar cell.
43. A method for producing an electrochemical element having a
Layer B/Layer A/Layer C, Layer B/Layer A/Layer B or Layer C/Layer
A/Layer C laminate structure which comprises the steps of (i)
providing a laminate comprising Layer A, Layer B and Layer C,
wherein Layer A is disposed between Layer B and Layer C, Layer A
comprises an ion conductive material, Layer B and Layer C each
comprises a material having an ion conductivity lower than that of
Layer A, and at least one of Layer B and Layer C comprises a non
electron-conductive material, (ii) removing at least one of Layer B
and Layer C from Layer A of the laminate, or removing Layer B or
Layer C having on the surface thereof facing Layer A a thin layer
comprising a metal, a metal oxide or carbon, together with said
thin layer from Layer A of said laminate, to produce a Layer
A/Layer C or Layer B/Layer A laminate, and (iii) laminating the
thus obtained laminate on a Layer A/Layer C or Layer B/Layer A
laminate produced in the same manner such that Layers A of the
respective laminates are bonded together.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This is a continuation-in-part of (1) U.S. application Ser.
No. 08/822,465, filed Mar. 21, 1997, which in turn claims benefit
of U.S. Provisional Application 60/014,567, filed Apr. 1, 1996 and
of Japanese Patent Application 8/93682, filed Mar. 21, 1996; and
(2) International Application PCT/JP97/00944, filed Mar. 21, 1997,
which claims benefit from Japanese Patent Application 8/93682,
filed Mar. 21, 1996.
FIELD OF THE INVENTION
[0002] The present invention relates to a laminate comprising an
ion conductive material such as a solid polymer electrolyte or
polymer gel electrolyte, and a method for producing an ion
conductive laminate. The present invention also relates to a method
for producing an electrochemical element and apparatus utilizing
the ion conductive laminate.
BACKGROUND OF THE INVENTION
[0003] To cope with the trend towards downsizing or solidification
in the field of ionics, a solid electrolyte material has been
proposed as a new ion conductive material in place of conventional
electrolytic solutions. Investigators have aggressively attempted
to apply the electrolyte material to solid primary or secondary
batteries, electrolytic capacitors, electrical double layer
capacitors, photoelectric cells, solar cells, fuel cells,
electrochromic elements, various sensors and antistatic film.
[0004] Conventional batteries using an electrolytic solution employ
a porous thin film separator impregnated with an electrolytic
solution. In this case, the production and processing cost of the
porous film is high which in turn increases the cost of
conventional batteries. Furthermore, the film is not capable of
holding the electrolytic solution. This causes the solution to leak
from the battery or causes the electrode substance to elute,
thereby giving rise to problems with respect to long-term
reliability and safety of the battery.
[0005] On the other hand, products using a solid electrolyte
material are generally free from the above-described problems and
are furthermore capable of providing a product having a reduced
thickness. Additionally, the solid electrolyte has excellent heat
resistance and is advantageously employed in the production of
products such as batteries. In particular, batteries employing a
solid electrolyte material containing a polymer as a constituent
component have better flexibility as compared with those using an
inorganic material, and are advantageous in that they can be formed
into various shapes.
[0006] As an example of a solid electrolyte material containing a
polymer as a constituent component (hereinafter also referred to as
a "solid polymer electrolyte" or "polymer gel electrolyte"), Br.
Polym. J., Vol. 319, page 137 (1975) describes a composite of a
polyethylene oxide with an inorganic alkali metal salt. However,
the ion conductivity thereof at room temperature is as low as
10.sup.-7 S/cm.
[0007] In recent years, a comb structure polymer has been reported
having introduced into the side chain thereof an oligooxyethylene
which elevates the thermal motility of the oxyethylene chain
bearing ion conductivity, to thereby improve the ion conductivity
of the polymer. For example, J. Phys. Chem., Vol. 89, page 987
(1984) describes a polymethacrylic acid having added to the side
chain thereof an oligooxyethylene compounded with an alkali metal
salt. Furthermore, J. Am. Chem. Soc., Vol. 106, page 6,854 (1984)
describes a polyphosphazene having an oligooxyethylene side chain
compounded with an alkali metal salt.
[0008] U.S. Pat. No. 4,357,401 describes a solid polymer
electrolyte having an ion conductivity at 50.degree. C. of
approximately from 10.sup.-4 to 10.sup.-5 S/cm which can be
obtained by compounding a metal salt with a cross-linked polymer
having reduced crystallinity. U.S. Pat. No. 4,792,504 proposes to
improve the ion conductivity by using a cross-linked solid polymer
electrolyte impregnated with an electrolytic solution comprising a
metal salt and an aprotic solvent in polyethylene oxide having a
continuous network.
[0009] Furthermore, in recent years, an electrical double layer
capacitor has been used, for example, as a memory backup power
source, where a carbon material having a large specific surface
area, such as activated carbon and carbon black, is used as a
polarizable electrode, and an ion conductive solution is deposited
between such electrodes. For example, Kino Zairyo (Functional
Materials), page 33 (February, 1989) describes a capacitor
employing a carbon-base polarizable electrode and an organic
electrolytic solution, and 173th Electrochemical Society Meeting,
Atlanta, Ga., No. 18 (May, 1988) describes an electrical double
layer capacitor using an aqueous sulfuric acid solution.
Furthermore, Japanese Unexamined Patent Publication (kokai) No.
63-244570 discloses a capacitor employing
Rb.sub.2Cu.sub.3I.sub.3Cl.sub.7 which has a high electrical
conductivity as an inorganic solid electrolyte.
[0010] However, electrical double layer capacitors using a known
electrolytic solution are bound to create problems with respect to
long-term use or reliability. This is because the solution readily
leaks from the capacitor under severe conditions such as when the
capacitor is used for a long period of time or when a high voltage
is applied thereto. On the other hand, electrical double layer
capacitors using a conventional inorganic ion conductive substance
are disadvantageous in that the decomposition voltage of the ion
conductive substance is low and the output voltage is low.
[0011] Japanese Unexamined Patent Publication (kokai) No. 4-253771
proposes to use a polyphosphazene-base polymer as an ion conductive
substance for batteries or electrical double layer capacitors. When
a solid ion conductive substance mainly comprising the
above-described polymer is used, the resulting advantages are that
the output voltage is relatively high as compared with that
obtained when an inorganic ion conductive substance is used, the
device can be formed into various shapes, and sealing is easy.
[0012] The solid polymer electrolyte under general investigation
has an improved ion conductivity of approximately from 10.sup.-4 to
10.sup.-5 S/cm. However, this is still in a low level that is two
orders of magnitude or more lower than the ion conductivity of a
liquid ion conductive material. Furthermore, the ion conductivity
considerably decreases at a temperature of 0.degree. C. and
below.
[0013] In order to improve ion conductivity, the polymers for use
in the solid polymer electrolyte have a low glass transition
temperature. If the glass transition temperature is lowered, a
problem arises in that the polymer has reduced mechanical strength
which causes difficulties in industrial handling. Furthermore, when
a solvent is added to further improve the ion conductivity, the
mechanical strength disadvantageously is further reduced.
[0014] The polymers for use in the solid polymer electrolyte
usually absorb water, and water absorptivity is a problem when used
in non-aqueous electrochemical elements such as lithium (ion)
batteries or electrical double layer capacitors.
[0015] In addition to the above described batteries and capacitors,
the ion conductive material is an important constituent material of
electrochemical devices such as electrochromic displays and power
generating apparatuses such as photoelectric cells and solar cells,
and as an electrochemical element for use in assembling these
devices such as electrochemical power generating elements,
electrochemical coloring elements and electrochemical
light-emitting elements. The ion conductive material is an
important constituent of antistatic materials which are capable of
eliminating undesirable electrostatic effects and can also be used
as a sensor material. However, the above described problems of
conventional ion conductive materials with respect to batteries or
capacitors are also encountered in the production of products for
these additional uses. Accordingly, there is a need to overcome the
above problems of the prior art, to develop solid polymer
electrolyte materials having excellent ion conductivity, and to
develop ion conductive materials which can be easily integrated
into an electrochemical element or electrochemical apparatus as a
solid polymer electrolyte.
SUMMARY OF THE INVENTION
[0016] An object of the present invention is to provide an ion
conductive material and a laminate thereof having excellent ion
conductivity at room temperature or at lower temperatures, a low
water content, sufficiently high mechanical strength and storage
stability to allow for practical handling, and a form which is
easily integrated into electrochemical elements or electrochemical
apparatuses.
[0017] Another object of the present invention is to provide a
method for producing the above described ion conductive
laminate.
[0018] Yet another object of the present invention is to provide a
method of producing an electrochemical apparatus having high
capability and excellent reliability including an electrochemical
element, an electrochemical power generating element, a coloring
element or a light-emitting element, such as a battery, an
electrical double layer capacitor, an electrochromic element, a
photoelectric cell and a solar cell, and an electrically conductive
material using the ion conductive laminate of the present
invention.
[0019] As a result of extensive investigations on the
above-described problems, the present inventors have discovered
that a laminate of a layer comprising an ion conductive material
and having provided on the upper part and the lower part thereof a
liquid-impermeable, particularly, water-impermeable layer
comprising a non electron-conductive material having an ion
conductivity lower than that of the ion conductive material, and a
liquid-impermeable, particularly, water-impermeable layer
comprising a material having an ion conductivity lower than the ion
conductive material, respectively, can overcome problems with
respect to atmosphere control or strength in industrial handling of
the ion conductive material. The present invention has been
accomplished based on this finding.
[0020] More specifically, the present invention provides a laminate
comprising an intermediate layer of an ion conductive material and
outer layers each comprising a non ion-conductive material, at
least one outer layer comprising a non electron-conductive
material; a laminate comprising an intermediate layer of an ion
conductive material, one outer layer comprising a non
ion-conductive material and another outer layer comprising a
material having an ion conductivity lower than that of the ion
conductive material in the intermediate layer, at least one outer
layer being a layer comprising a non electron-conductive material;
or a laminate comprising an intermediate layer of an ion conductive
material and outer layers each comprising a material having an ion
conductivity lower than that of the ion conductive material in the
intermediate layer, at least one outer layer being a layer
comprising a non electron-conductive material; and a production
method thereof. Furthermore, the present invention provides a
method of using the above-described laminates, where the ion
conductive material held in the laminate can be industrially
handled more easily than conventional materials, to produce various
electrochemical apparatuses while keeping its excellent quality; a
method, according to the above-described method of use, for
producing an electrochemical apparatus including an electrochemical
element, an electrochemical power generating element, a coloring
element and a light-emitting element, such as a battery, a
capacitor, an electrochromic display, a photoelectric cell and a
solar cell; and a method for producing an electrically conductive
material using the above-described laminate.
[0021] The present invention relates to the following structures
and methods:
[0022] (1) A laminate comprising Layer A, Layer B and Layer C,
wherein Layer A is disposed between Layer B and Layer C, Layer A
comprises an ion conductive material, Layer B and Layer C each
comprises a material having an ion conductivity lower than that of
Layer A, and at least one of Layer B and Layer C comprises a non
electron-conductive material.
[0023] (2) The laminate as described in (1) above, wherein at least
one of Layer B and Layer C has a contact angle of 80.degree. or
less with polyethylene glycol having an average molecular weight of
about 400.
[0024] (3) The laminate as described in (1) above, wherein at least
one of Layer B and Layer C has a contact angle of 60.degree. or
less with polyethylene glycol having an average molecular weight of
about 400.
[0025] (4) The laminate as described in any one of (1) to (3)
above, wherein Layer B and Layer C each is a liquid impermeable
layer.
[0026] (5) The laminate as described in any one of (1) to (4)
above, wherein Layer B and Layer C each is a water impermeable
layer.
[0027] (6) The laminate as described in any one of (1) to (5)
above, wherein at least one of Layer B and Layer C comprises a
material having a dielectric constant of 8 or less.
[0028] (7) The laminate as described in any one of (1) to (6)
above, wherein at least one of Layer B and Layer C has an ion
conductivity that is one tenth the ion conductivity of Layer A or
less.
[0029] (8) The laminate as described in any one of (1) to (7)
above, wherein at least one of Layer B and Layer C comprises a
thermoplastic resin or a composition containing a thermoplastic
resin.
[0030] (9) The laminate as described in any one of (1) to (7)
above, wherein at least one of Layer B and Layer C comprises an
engineering plastic, a thermosetting resin or a composition
containing one of an engineering plastic or a thermosetting
resin.
[0031] (10) The laminate as described in any one of (1) to (9)
above, wherein the ion conductive material of Layer A has a
specific resistivity of 10.sup.6 .OMEGA..multidot.cm or less.
[0032] (11) The laminate as described in any one of (1) to (9)
above, wherein the ion conductive material of Layer A has a
specific resistivity of 10.sup.5 .OMEGA..multidot.cm or less.
[0033] (12) The laminate as described in any one of (1) to (11)
above, wherein Layer A has a thickness of from 0.1 to 1,000
.mu.m.
[0034] (13) The laminate as described in any one of (1) to (12)
above, wherein Layer A has a water content of 200 ppm or less.
[0035] (14) The laminate as described in any one of (1) to (13)
above, wherein Layer A has a peel strength such that Layer B or
Layer C can be peeled off without substantially deforming the shape
of Layer A.
[0036] (15) The laminate as described in any one of (1) to (14)
above, wherein at least one of Layer B and Layer C is a light
transmissible layer.
[0037] (16) The laminate as described in any one of (1) to (14)
above, wherein none of Layer B and Layer C are light-transmissible
layers.
[0038] (17) The laminate as described in any one of (1) to (16)
above, wherein both Layer B and Layer C are gas impermeable
layers.
[0039] (18) The laminate as described in any one of (1) to (17)
above, wherein Layer B or Layer C comprises an electron conductive
material, and the electron conductive material-containing layer is
connected to an electron conductive electric conductor.
[0040] (19) The laminate as described in any one of (1) to (17)
above, wherein electron conductive electric conductors are
connected to two different sites of Layer A.
[0041] (20) The laminate as described in any one of (1) to (19)
above, wherein Layer A comprises a material containing a
cross-linked polymer as a constituent component.
[0042] (21) The laminate as described in any one of (1) to (19)
above, wherein Layer A comprises a material containing a
cross-linked polymer having at least one alkyleneoxy-containing
chain in the main chain and/or in the side chain thereof as a
constituent component.
[0043] (22) The laminate as described in any one of (1) to (19)
above, wherein Layer A comprises a material containing a
cross-linked polymer having at least one alkyleneoxy-containing
chain and at least one --NH--C(.dbd.O)--O-- bond in the main chain
and/or in the side chain thereof as a constituent component.
[0044] (23) The laminate as described in any one of (1) to (19)
above, wherein Layer A comprises a material containing, as a
constituent component, a polymer of a (meth)acryloyl-base compound
having a structure substituted by at least one unit represented by
formula (1) and/or a copolymer containing said compound as a
copolymer component:
CH.sub.2.dbd.C(R.sup.1)CO[O(CH.sub.2).sub.x(CH(CH.sub.3)).sub.y].sub.zNHCO-
O--R.sup.2-- (1)
[0045] wherein R.sup.1 represents hydrogen or an alkyl group,
R.sup.2 represents a divalent organic group containing an
oxyalkylene group, the organic group may have any of linear,
branched and cyclic structures and may contain one or more elements
other than carbon, hydrogen and oxygen, x and y each represents 0
or an integer of from 1 to 5, z represents 0 or a numerical value
of from 1 to 10, provided that when both of x and y are zero, z is
zero, the moiety (CH.sub.2) and the moiety (CH(CH.sub.3)) may be
randomly configured, provided that when two or more units
represented by formula (1) are present in the same molecule,
R.sup.1 and R.sup.2 of one unit may be different from R.sup.1 and
R.sup.2 of the other units, and the values x, y and z of one unit
may be different from the values x, y and z of the other units.
[0046] (24) The laminate as described in any one of (1) to (23)
above, wherein the ion conductive material of Layer A contains an
electrolyte salt and/or a solvent.
[0047] (25) The laminate as described in (24) above, wherein the
electrolyte salt is at least one selected from the group consisting
of an alkali metal salt, a quaternary ammonium salt and a
quaternary phosphonium salt.
[0048] (26) The laminate as described in (24) or (25) above,
wherein the solvent is at least one selected from the group
consisting of a carbonate-base compound, a lactone-base compound
and an ether-base compound, each having a dielectric constant of 1
or more.
[0049] (27) The laminate as described in any one of (1) to (26)
above, further comprising a thin layer comprising a metal, a metal
oxide or carbon which is present between Layer A and Layer B and/or
between Layer A and Layer C.
[0050] (28) The laminate as described in any one of (1) to (27)
above, further comprising an electron conductive thin layer which
is present between Layer A and either one of Layer B and Layer C,
and the other of Layer B and Layer C comprises a non
electron-conductive material.
[0051] (29) The laminate as described in (27) or (28) above,
wherein the thin layer is connected to an electron conductive
electric conductor.
[0052] (30) A method for producing the laminate described in any
one of (1) to (26) above, comprising the steps of (i) laminating
Layer A on Layer B in such manner that the material of Layer A
substantially does not flow or move on Layer B, to provide a
laminate structure consisting of Layer B/Layer A, wherein Layer A
comprises an ion conductive material and Layer B comprises a
material having an ion conductivity lower than that of Layer A,
(ii) laminating Layer C on Layer A to provide a laminate structure
consisting of Layer B/Layer A/Layer C, wherein Layer C comprises a
material having an ion conductivity lower than that of Layer A, and
(iii) then applying pressure to the laminate structure with a force
applied on the Layer B side surface and a force in opposition
thereto applied on the Layer C side surface.
[0053] (31) A method for producing the laminate described in any
one of (1) to (26) above, comprising the steps of (i) laminating
Layer A on Layer B in such manner that the material of Layer A
substantially does not flow or move on Layer B, to provide a
laminate structure consisting of Layer B/Layer A, wherein Layer A
comprises an ion conductive material containing a curable substance
and Layer B comprises a material having an ion conductivity lower
than that of Layer A, (ii) laminating Layer C on Layer A to provide
a laminate structure consisting of Layer B/Layer A/Layer C, wherein
Layer C comprises a material having an ion conductivity lower than
that of Layer A, and (iii) then applying pressure to the laminate
structure with a force applied on the Layer B side surface and a
force in opposition thereto applied on the Layer C side
surface.
[0054] (32) A method for producing the laminate described in any
one of (1) to (26) above, comprising the steps of (i) laminating
Layer A on Layer B in such manner that the material of Layer A
substantially does not flow or move on Layer B, to provide a
laminate structure consisting of Layer B/Layer A, wherein Layer A
comprises an ion conductive material containing a curable substance
and Layer B comprises a material having an ion conductivity lower
than that of Layer A, (ii) heating and/or irradiating the laminate
structure with active light to cure Layer A, (iii) laminating Layer
C on Layer A to provide a laminate structure consisting of Layer
B/Layer A/Layer C, wherein Layer C comprises a material having an
ion conductivity lower than that of Layer A, and (iv) then applying
pressure to the laminate structure with a force applied on the
Layer B side surface and a force in opposition thereto applied on
the Layer C side surface.
[0055] (33) The method for producing a laminate according to any
one of (30) to (32) above, wherein the laminate is heated and/or
irradiated with active light before or during the pressure applying
step.
[0056] (34) The method for producing a laminate according to any
one of (30) to (33) above, wherein the laminate structure
consisting of Layer B/Layer A comprises Layer A substantially in a
non-flowable state as a constituent layer which is obtained by
laminating Layer A comprising an ion conductive material containing
a solvent on Layer B comprising a material having an ion
conductivity lower than that of Layer A in such manner that the
material of Layer A substantially does not flow or move on Layer B
and then removing the solvent.
[0057] (35) A method for producing the laminate described in any
one of (1) to (26) above, comprising the steps of (i) forming a
thin layer D.sub.1 comprising a metal, a metal oxide or carbon on
one surface of Layer B, (ii) laminating Layer A on the thin layer
D.sub.1 in such manner that the material of Layer A substantially
does not flow or move on the thin layer D.sub.1, to provide a
laminate structure consisting of Layer B/thin layer D.sub.1/Layer
A, (iii) laminating Layer C on Layer A to provide a laminate
structure consisting of Layer B/thin layer D.sub.1/Layer A/Layer C,
and (iv) then applying pressure to the laminate structure with a
force applied on the Layer B side surface and a force in opposition
thereto applied on the Layer C side surface, wherein Layer A
comprises an ion conductive material and Layer B and Layer C each
comprises a material having an ion conductivity lower than that of
Layer A.
[0058] (36) A method for producing the laminate described in any
one of (1) to (26) above, comprising the steps of (i) forming a
thin layer D.sub.2 comprising a metal, a metal oxide or carbon on
one surface of Layer C, (ii) laminating on the thin layer D.sub.2
the Layer A surface of a laminate structure consisting of Layer
B/Layer A obtained by laminating Layer A on Layer B in such manner
that the material of Layer A substantially does not flow or move on
Layer B, to provide a laminate structure consisting of Layer C/thin
layer D.sub.2/Layer A/Layer B, and (iii) then applying pressure to
the laminate structure with a force applied on the Layer B side
surface and a force in opposition thereto applied on the Layer C
side surface, wherein Layer A comprises an ion conductive material
and Layer B and Layer C each comprises a material having an ion
conductivity lower than that of Layer A.
[0059] (37) A method for producing the laminate described in any
one of (1) to (26) above, comprising the steps of (i) forming a
thin layer D.sub.1 comprising a metal, a metal oxide or carbon on
one surface of Layer B, (ii) laminating Layer A on the thin layer
D.sub.1 in such manner that the material of Layer A substantially
does not flow or move on the thin layer, to provide a laminate
structure consisting of Layer B/thin layer D.sub.1/Layer A, (iii)
laminating Layer C on Layer A to provide a laminate structure
consisting of Layer B/thin layer D.sub.1/Layer A/Layer C, and (iv)
then applying pressure to the laminate structure with a force
applied on the Layer B side surface and a force in opposition
thereto applied on the Layer C side surface, wherein Layer A
comprises an ion conductive material containing a curable substance
and Layer B and Layer C each comprises a material having an ion
conductivity lower than that of Layer A
[0060] (38) A method for producing the laminate described in any
one of (1) to (26) above, comprising the steps of (i) forming a
thin layer D.sub.2 comprising a metal, a metal oxide or carbon on
one surface of Layer C, (ii) laminating on the thin layer D.sub.2
the Layer A surface of a laminate structure consisting of Layer
B/Layer A obtained by laminating Layer A on Layer B in such manner
that the material of Layer A substantially does not flow or move on
Layer B, to provide a laminate structure consisting of Layer C/thin
layer D.sub.2/Layer A/Layer B, and (iii) then applying pressure to
the laminate structure with a force applied on the Layer B side
surface and a force in opposition thereto applied on the Layer C
side surface, wherein Layer A comprises an ion conductive material
containing a curable substance and Layer B and Layer C each
comprises a material having an ion conductivity lower than that of
Layer A.
[0061] (39) A method for producing the laminate described in any
one of (1) to (26) above, comprising the steps of (i) forming a
thin layer D.sub.1 comprising a metal, a metal oxide or carbon on
one surface of Layer B, (ii) laminating Layer A on the thin layer
D.sub.1 in such manner that the material of Layer A substantially
does not flow or move on the thin layer D.sub.1, to provide a
laminate structure consisting of Layer B/thin layer D.sub.1/Layer
A, wherein Layer A comprises an ion conductive material containing
a curable substance and Layer B comprises a material having an ion
conductivity lower than that of Layer A, (iii) heating and/or
irradiating the laminate structure with active light to cure Layer
A, (iv) laminating Layer C on Layer A to provide a laminate
structure consisting of Layer B/thin layer D.sub.1/Layer A/Layer C,
wherein Layer C comprises a material having an ion conductivity
lower than that of Layer A, and (v) then applying pressure to the
laminate structure with a force applied on the Layer B side surface
and a force in opposition thereto applied on the Layer C side
surface.
[0062] (40) A method for producing the laminate described in any
one of (1) to (26) above, comprising the steps of (i) laminating
Layer A on Layer B in such manner that the material of Layer A
substantially does not flow or move on Layer B, to provide a
laminate structure consisting of Layer B/Layer A, wherein Layer A
comprises an ion conductive material containing a curable substance
and Layer B comprises a material having an ion conductivity lower
than that of Layer A, (ii) heating and/or irradiating the laminate
structure with active light to cure Layer A, (iii) laminating the
thin layer D.sub.2 surface of Layer C having on one surface thereof
a thin layer D.sub.2 comprising a metal, a metal oxide or carbon,
to provide a laminate structure consisting of Layer C/thin layer
D.sub.2/Layer A/Layer B, wherein Layer C comprises a material
having an ion conductivity lower than that of Layer A, and (iv)
then applying pressure to the laminate structure with a force
applied on the Layer B side surface and a force in opposition
thereto applied on the Layer C side surface.
[0063] (41) A method for producing an electrochemical element which
comprises (i) removing at least one of Layer B and Layer C from
Layer A of the laminate described in any one of (1) to (29) above,
or removing Layer B or Layer C having on the surface thereof facing
Layer A a thin layer comprising a metal, a metal oxide or carbon,
together with the thin layer from Layer A of the laminate, and (ii)
forming a layer comprising a material containing an
electrochemically-active substance on at least one removal surface
of Layer A.
[0064] (42) A method for producing an electrochemical power
generating element which comprises (i) removing at least one of
Layer B and Layer C from Layer A of the laminate described in any
one of (1) to (29) above, or removing Layer B or Layer C having on
the surface thereof facing Layer A a thin layer comprising a metal,
a metal oxide or carbon, together with the thin layer from Layer A
of the laminate, and (ii) forming a layer comprising a material
containing an electrochemically-active substance on at least one
removal surface of Layer A.
[0065] (43) A method for producing an electrochemical coloring
element which comprises (i) removing at least one of Layer B and
Layer C from Layer A of the laminate described in any one of (1) to
(29) above, or removing Layer B or Layer C having on the surface
thereof facing Layer A a thin layer comprising a metal, a metal
oxide or carbon, together with the thin layer from Layer A of the
laminate, and (ii) forming a layer comprising a material containing
an electrochemically-active substance on at least one removal
surface of Layer A.
[0066] (44) A method for producing an electrochemical
light-emitting element which comprises (i) removing at least one of
Layer B and Layer C from Layer A of the laminate described in any
one of (1) to (29) above, or removing Layer B or Layer C having on
the surface thereof facing Layer A a thin layer comprising a metal,
a metal oxide or carbon, together with the thin layer from Layer A
of the laminate, and (ii) forming a layer comprising a material
containing an electrochemically-active substance on at least one
removal surface of Layer A.
[0067] (45) A method for producing a battery which comprises (i)
removing at least one of Layer B and Layer C from Layer A of the
laminate described in any one of (1) to (29) above, or removing
Layer B or Layer C having on the surface thereof facing Layer A a
thin layer comprising a metal, a metal oxide or carbon, together
with the thin layer from Layer A of the laminate, and (ii) forming
a layer comprising a material containing an
electrochemically-active substance on at least one removal surface
of Layer A.
[0068] (46) A method for producing a capacitor which comprises (i)
removing at least one of Layer B and Layer C from Layer A of the
laminate described in any one of (1) to (29) above, or removing
Layer B or Layer C having on the surface thereof facing Layer A a
thin layer comprising a metal, a metal oxide or carbon, together
with the thin layer from Layer A of the laminate, and (ii) forming
a layer comprising a material containing an
electrochemically-active substance on at least one removal surface
of Layer A.
[0069] (47) A method for producing an electrochromic element which
comprises (i) removing at least one of Layer B and Layer C from
Layer A of the laminate described in any one of (1) to (29) above,
or removing Layer B or Layer C having on the surface thereof facing
Layer A a thin layer comprising a metal, a metal oxide or carbon,
together with the thin layer from Layer A of the laminate, and (ii)
forming a layer comprising a material containing an
electrochemically-active substance on at least one removal surface
of Layer A.
[0070] (48) A method for producing a photoelectric cell which
comprises (i) removing at least one of Layer B and Layer C from
Layer A of the laminate described in any one of (1) to (29) above,
or removing Layer B or Layer C having on the surface thereof facing
Layer A a thin layer comprising a metal, a metal oxide or carbon,
together with the thin layer from Layer A of the laminate, and (ii)
forming a layer comprising a material containing an
electrochemically-active substance on at least one removal surface
of Layer A.
[0071] (49) A method for producing a solar cell which comprises (i)
removing at least one of Layer B and Layer C from Layer A of the
laminate described in any one of (1) to (29) above, or removing
Layer B or Layer C having on the surface thereof facing Layer A a
thin layer comprising a metal, a metal oxide or carbon, together
with the thin layer from Layer A of the laminate, and (ii) forming
a layer comprising a material containing an
electrochemically-active substance on at least one removal surface
of Layer A.
[0072] (50) A method for producing an electrochemical element
having a Layer B/Layer A/Layer C, Layer B/Layer A/Layer B or Layer
C/Layer A/Layer C laminate structure comprising (i) removing at
least one of Layer B and Layer C from Layer A of the laminate
described in any one of (1) to (29) above, or removing Layer B or
Layer C having on the surface thereof facing Layer A a thin layer
comprising a metal, a metal oxide or carbon, together with the thin
layer from Layer A of the laminate, to produce a Layer A/Layer C or
Layer B/Layer A laminate, and (ii) laminating the thus obtained
laminate on a Layer A/Layer C or Layer B/Layer A laminate produced
in the same manner such that Layers A of the respective laminates
are bonded together.
BRIEF DESCRIPTION OF THE DRAWINGS
[0073] FIG. 1 is a schematic cross section of the laminate in one
example of the present invention.
[0074] FIG. 2 is a schematic cross section of the laminate in one
example of the present invention.
[0075] FIG. 3 is a schematic cross section of the laminate in one
example of the present invention.
[0076] FIG. 4 is a schematic cross section of the laminate in one
example of the present invention.
[0077] FIG. 5 is a schematic cross section of the laminate in one
example of the present invention.
[0078] FIG. 6 is a schematic cross section of the laminate in one
example of the present invention.
[0079] FIG. 7 is a schematic cross section of the laminate in one
example of the present invention.
[0080] FIG. 8 is a schematic cross section of the laminate in one
example of the present invention.
[0081] FIG. 9 is a schematic cross section of one example of a thin
film solid secondary battery produced according to the present
invention.
[0082] FIG. 10 is a schematic cross section of one example of a
solid electrical double layer capacitor produced according to the
present invention.
[0083] FIG. 11 is a schematic cross section of a battery prepared
in the following Examples.
[0084] FIG. 12 is a schematic cross section of a battery prepared
in the following Examples.
[0085] FIG. 13 is a schematic cross section of a solid electrical
double layer capacitor prepared in the following Examples.
[0086] FIG. 14 is a schematic cross section of an ECD prepared in
the following Examples.
[0087] FIG. 15 is a schematic cross section of a solid wet-type
solar cell (photoelectrochemical solar cell) prepared in the
following Examples.
[0088] The symbols used in FIGS. 1 to 15 (letters or numerals) each
has the following meaning:
[0089] A Layer A: ion conductive material layer
[0090] B Layer B: layer comprising a material having an ion
conductivity lower than that of Layer A
[0091] C Layer C: layer comprising a material having an ion
conductivity lower than that of Layer A
[0092] D.sub.1 thin layer D.sub.1 comprising a metal, a metal oxide
or carbon
[0093] D.sub.2 thin layer D.sub.2 comprising a metal, a metal oxide
or carbon
[0094] E.sub.1 electron conductive electric conductor
[0095] E.sub.2 electron conductive electric conductor
[0096] 1 positive electrode
[0097] 2 solid polymer electrolyte or polymer gel electrolyte
[0098] 3 negative electrode
[0099] 4 current collecting body
[0100] 5 insulating spacer
[0101] 6 insulating resin sealant
[0102] 7 polarizable electrode
[0103] 8 lead wire
[0104] 9 glass
[0105] 10 transparent electrically conductive layer
[0106] 11 electrochromic layer
[0107] 12 counter electrode
[0108] 13 electrode
[0109] 14 electrode
[0110] 15 substrate A
[0111] 16 substrate B
DETAILED DESCRIPTION OF THE INVENTION
[0112] The present invention is described in detail below.
[0113] The ion conductive material for use in the ion conductive
laminate of the present invention includes a substance having an
ion conductivity (ion conductive substance), a mixture or composite
containing an ion conductive substance, a mixture or composite
containing an ionic substance and an ion conductive substance, and
a material containing the above-described mixture or composite and
in addition, a curable substance, a solvent, an additive, a filler
or other additives, which material is capable of exhibiting ion
conductivity. The ion conductive material may be in the form of any
of a liquid, sol, solid and gel. The ion conductive material for
use in the laminate of the present invention includes, depending
upon its intended application, a material comprising a so-called
precursor which is converted to acquire more preferred ion
conductive properties or has physical or chemical properties which
have been changed, for example, by heating, irradiating with active
light or removing solvent.
[0114] The term "ionic substance" as used herein means a substance
which provides an ion as a carrier for conducting electricity, and
in which an applied electric field causes a current to flow by
moving an electric charge. Examples thereof include substances
containing various ionic species as a component, such as alkali
metal salts, quaternary ammonium salts, quaternary phosphonium
salts, transition metal salts, protonic acids and polyelectrolyte
salts. As the ionic substance, any ionic substance such as
electrolyte salts generally used in batteries, capacitors and
electrochromic elements may be suitably used. Specific examples
thereof include polyelectrolyte salts such as alkali metal salts,
quaternary ammonium salts, quaternary phosphonium salts and
transition metal salts, and protonic acids, which are described
below with respect to electrochemical elements or apparatuses such
as batteries and capacitors.
[0115] Examples of the alkali metal salts for use as an electrolyte
salt include LiCF.sub.3SO.sub.3, LiPF.sub.6, LiClO.sub.4, LiI,
LiBF.sub.4, LiSCN, LiAsF.sub.6, LiN(CF.sub.3SO.sub.2).sub.2,
NaCF.sub.3SO.sub.3, NaPF.sub.6, NaClO.sub.4, NaI, NaBF.sub.4,
NaAsF.sub.6, KCF.sub.3SO.sub.3, KPF.sub.6 and KI. Examples of the
electrolyte salt such as quaternary ammonium salts, quaternary
phosphonium salts and transition metal salts, and the protonic acid
include quaternary ammonium salts such as (CH.sub.3).sub.4NBF.sub.4
and (CH.sub.3CH.sub.2).sub.4NClO.sub.4, transition metal salts such
as AgClO.sub.4, quaternary phosphonium salts such as
(CH.sub.3).sub.4PBF.sub.4, organic acids and salts thereof such as
p-toluenesulfonic acid, and inorganic acids such as hydrochloric
acid and sulfuric acid.
[0116] When the ion conductive material as Layer A of the laminate
of the present invention is used as a solid polymer electrolyte
(the term "solid polymer electrolyte" may hereinafter be referred
to as "SPE" in short) or polymer gel electrolyte (the term "polymer
gel electrolyte" may hereinafter be referred to as "PGE" in short)
in an electrochemical apparatus, for example, in a secondary
battery, the alkali metal is preferably lithium or a lithium alloy
in view of high voltage and high capacity and the capability to
reduce thickness. Accordingly, the alkali metal salt is preferably
a lithium salt. When the negative electrode of the battery is a
carbon material negative electrode, not only alkali metal ions but
also quaternary ammonium salts, quaternary phosphonium salts,
transition metal salts and various protonic acids may be used. When
the ion conductive material as Layer A of the laminate of the
present invention is used as a SPE or PGE in a solid electrical
double layer capacitor, the kind of electrolyte salt used in the
compounding is not particularly limited, and compounds containing
an ion intended to be a charge carrier may be used. However, the
compound preferably contains an ion having a large dissociation
constant in a SPE or PGE and is capable of readily forming an
electrical double layer with a polarizable electrode. Examples of
the compound include quaternary ammonium salts such as
(CH.sub.3).sub.4NBF.sub.4 and (CH.sub.3CH.sub.2).sub.4NClO.sub.4,
transition metal salts such as AgClO.sub.4, quaternary phosphonium
salts such as (CH.sub.3).sub.4PBF.sub.4, alkali metal salts such as
LiCF.sub.3SO.sub.3, LiPF.sub.6, LiClO.sub.4, LiI, LiBF.sub.4,
LiSCN, LiAsF.sub.6, LiN(CF.sub.3SO.sub.2).sub.2,
NaCF.sub.3SO.sub.3, NaPF.sub.6, NaClO.sub.4, NaI, NaBF.sub.4,
NaAsF.sub.6, KCF.sub.3SO.sub.3, KPF.sub.6 and KI, organic acids and
salts thereof such as p-toluenesulfonic acid, and inorganic acids
such as hydrochloric acid and sulfuric acid. Among these, preferred
in view of high output voltage and their large dissociation
constant are quaternary ammonium salts, quaternary phosphonium
salts and alkali metal salts. Among quaternary ammonium salts,
those having different substituents on the nitrogen of the ammonium
ion are preferred, such as (CH.sub.3CH.sub.2)(CH.sub.3CH.sub.2CH-
.sub.2CH.sub.2).sub.3NBF.sub.4, because of their high solubility or
dissociation constant in the SPE or PGE.
[0117] In the ion conductive material constituting Layer A, the
mixing amount of the ionic substance such as the above-described
electrolyte salt varies depending upon the polymer or other
components to be mixed, and also depends upon the intended purpose
of the laminate. However, if the mixing amount is too small, the
number of ion carriers is deficient, whereas if it is too large,
the mobility is lowered to thereby reduce the ion conductivity.
Accordingly, the mixing amount in the ion conductive material is
preferably from 0.1 to 70 wt %, more preferably from 1 to 50 wt %,
of the total amount of the polymer and the ionic substance.
[0118] The ion conductive substance is a substance which exhibits
electrical conduction in the presence of ions as a carrier for
carrying electricity. The ions move within a solution or solid
constituting the ion conductive substance under an applied electric
field. As a result, current flows through the ion conductive
substance. For example, the above-described ionic substance itself
is one type of ion conductive substance. Other examples of the ion
conductive substance include an ion conductive inorganic compound
such as LiSiCON and NaSiCON, a derivative thereof, a mixture or
composite of the inorganic compound with a polymer, an ionic
polymer substance (a so-called polyelectrolyte) such as nafion,
polystyrenesulfonic acid and a derivative thereof, and other
polymers capable of exhibiting the above-described ion conductive
electrical conduction. In the ion conductive laminates of the
present invention, the production methods thereof and various
usages using the laminate, polymers among the above-described
substances which are capable of exhibiting electrical conduction by
ion conduction are particularly preferred. Any polymer may be
suitably used in the ion conductive laminate of the present
invention if it is capable of exhibiting ion conductive electrical
conduction.
[0119] The ion conductive material constituting Layer A of the ion
conductive laminate of the present invention is particularly
preferably a material comprising a SPE, a PGE or a precursor
material thereof containing, as a constituent component, a polymer
capable of exhibiting the above-described ion conductive electrical
conduction. Additionally, in the SPE or PGE, ion conductive
polymers which can dissolve or dissociate the ionic substance such
as an electrolyte salt or which can absorb an electrolytic solution
are more preferably used in view of the ion conductivity of Layer A
or in view of electrochemical stability when used in an
electrochemical element or apparatus. Those polymers having a
dielectric constant higher than that of a saturated linear
hydrocarbon type polymer and having one or more kinds of hetero
atoms other than carbon and hydrogen in the main chain repeating
unit and/or in the side chain are preferred, and those having a low
glass transition temperature are more preferred. Examples thereof
include polyethylene oxide, polypropylene oxide, an ethylene
oxide/propylene oxide copolymer, a derivative, a graft form and a
cross-linked form thereof; polymers having the above-mentioned
polyalkylene oxide chain in the main chain and/or in side chain
thereof; polysiloxane, polyphosphazene, poly(meth)acrylic ester,
polyacrylonitrile, latex and a derivative thereof; and polymers
having an ion conductivity and having at least one of O, N and S
atoms in the repeating unit and/or in the side chain thereof.
[0120] In the specification of the present invention, the term
"(meth)acryl . . . " is a generic term including "methacryl . . . "
and "acryl . . . ", and the term "alkyleneoxy" and "oxyalkylene"
have the same meaning.
[0121] Other preferred examples of the ion conductive polymer
include polymers and copolymers of the following functional monomer
or oligomer which is a precursor of the ion conductive polymer, and
cross-linked form thereof.
[0122] A (meth)acryloyl-base compound having at least one unit
represented by the following formula (1) in one molecule such as
N-(meth)acryloylcarbamic acid .omega.-methyl oligooxyethyl ester
and (meth)acryloyloxyethylcarbamic acid .omega.-methyl
oligooxyethyl ester, (hereinafter, the compound is referred to as
urethane (meth)acrylate having an oxyalkylene chain):
CH.sub.2.dbd.C(R.sup.1)CO[O(CH.sub.2).sub.x(CH(CH.sub.3)).sub.y].sub.zNHCO-
O--R.sup.2-- (1)
[0123] wherein R.sup.1 represents hydrogen or a methyl group,
R.sup.2 represents a divalent organic group containing an
oxyalkylene group, the organic group may have any of linear,
branched and cyclic structures or may contain one or more elements
other than carbon, hydrogen and oxygen, x and y each represents 0
or an integer of from 1 to 5, z represents 0 or a numerical value
of from 1 to 10, provided that when both of x and y are zero, z is
zero, the moiety (CH.sub.2) and the moiety (CH(CH.sub.3)) may be
randomly configured, provided that when two or more units
represented by formula (1) are present in the same molecule,
R.sup.1 and R.sup.2 of one unit may be different from R.sup.1 and
R.sup.2 of the other units, and the values x, y and z of one unit
may be different from the values x, y and z of the other units.
[0124] Further included are the various urethane acrylates
described in Radiation Curing: August, 1986, page 4 et seq., such
as phenylglycidylether acrylate hexamethylene diisocyanate urethane
prepolymer and phenylglicydylether acrylate isophorone diisocyanate
urethane prepolymer produced by Kyoei Sha Yushi Kagaku Kogyo and
others; (meth)acrylic ester and di(meth)acrylic ester each having
an oxyalkylene chain (e.g., methacrylic acid .omega.-methyl
oligooxyethyl ester), alkyl (meth)acrylates such as methyl
methacrylate and n-butyl acrylate; (meth)acrylamide-base compounds
such as acrylamide, methacrylamide, N,N-dimethylacrylamide,
N,N-dimethylmethacrylamide, acryloylmorpholine,
methacryloylmorpholine and N,N-dimethylaminopropyl(meth)acrylamide;
N-vinylamide-base compounds such as N-vinylacetamide and
N-vinylformamide; alkyl vinyl ethers such as ethyl vinyl ether; and
polyfunctional (meth)acrylates such as hexamethylene
di(meth)acrylate, timethylolpropane tri(meth)acrylate,
pentaerythritol penta(meth)acrylate and dipentaerythritol
hexa(meth)acrylate.
[0125] Preferred among these are urethane (meth)acrylates having an
oxyalkylene chain, other various urethane acrylates, (meth)acrylate
having an oxyalkylene chain and (meth)acrylamide-base compounds.
Among these, considering that a larger number of urethane groups or
oxyalkylene groups can be introduced into the polymer, urethane
(meth)acrylates having an oxyalkylene chain are more preferred.
[0126] The polymer or copolymer of various functional monomers or
oligomers described above, or a polymeric cross-linked form thereof
is used as the ion conductive substance constituting Layer A of the
laminate of the present invention. However, a layer containing a
curable substance such as the above-described functional monomer or
oligomer which is a precursor of the ion conductive substance
constituting Layer A may be formed, and then the monomer or
oligomer may be cured by polymerization or the like to convert the
same into a polymer, a copolymer or a polymeric cross-linked form.
When the polymer thus obtained contains an ionic substance or an
electrolytic solution, in order to maintain the mechanical strength
of the ion conductive material, the polymer is particularly
preferably a polymeric cross-linked form. In producing the
above-described ion conductive substance constituting Layer A or in
curing the precursor material of Layer A by polymerization or the
like to form Layer A, the polymerization of various functional
monomers or oligomers described above is preferably performed by
mixing therein at least one polyfunctional monomer or oligomer so
as to obtain an ion conductive substance in a polymeric
cross-linked form. The polyfunctional monomer or oligomer is
particularly preferably selected from bi- or greater functional
monomers or oligomers among the above-described functional monomers
or oligomers. In addition, for example, a mixture of divinyl
benzene, diol or polyol with diisocyanate or a polyfunctional
isocyanate, or a cross-linking monomer or oligomer having a
plurality of functional groups such as a vinyl group, an amino
group, an isocyanate group and an epoxy group, may be appropriately
used according to the objective capability.
[0127] The polymer, which is an important constituent component of
the ion conductive material constituting Layer A of the ion
conductive laminate of the present invention, is particularly
preferably a polymer, more preferably a copolymer or a polymeric
cross-linked form, containing as a monomer component, of the
above-described urethane (meth)acrylates having an oxyalkylene
chain, a urethane (meth)acrylate having an oxyalkylene chain and
having a structure where the hydrogen atoms of at least two
hydroxyl groups of a trihydric or greater polyhydric alcohol each
is substituted by any unit represented by formula (1). In
particular, the use of a polymer, preferably a copolymer or a
polymeric cross-linked form, containing, as a monomer component, a
urethane (meth)acrylate having an oxyalkylene chain substituted by
three or more of the above-described units is very preferred in
view of mechanical properties such as film strength, ion conductive
properties and stability of the ion conductive material formed.
[0128] In Layer A of the ion conductive laminate of the present
invention, a mixture of two or more of the above-described polymers
may be used as a constituent material.
[0129] In the urethane (meth)acrylate having an oxyalkylene chain
which is a particularly preferable functional monomer or oligomer
which is used to obtain an ion conductive material constituting
layer A of the ion conductive laminate of the present invention,
the number of oxyalkylene units (namely, the total number of
oxyalkylene units contained in R.sup.2 in formula (1)) in one
structural unit derived from the compound having a structure
substituted by the unit represented by formula (1) is preferably
from 1 to 1,000, more preferably from 5 to 200.
[0130] In the unit represented by formula (1):
CH.sub.2.dbd.C(R.sup.1)CO[O(CH.sub.2).sub.x(CH(CH.sub.3)).sub.y].sub.zNHCO-
O--R.sup.2-- (1)
[0131] (a) when x is 0 or 1, y is 0 or 1 and z is 0 or 1 (provided
that when both of x and y are zero, z is zero), the compound is
liquid and advantageous in that the viscosity is low and reaction
in a solvent system is easy.
[0132] On the other hand, in the above-described urethane
(meth)acrylate having an oxyalkylene chain, which is one of the
constituent materials of a SPE constituting Layer A of the ion
conductive laminate of the present invention, when
[0133] (b) x=2 to 5, y=0 and z=1 to 10,
[0134] (c) x=1 to 5, y=1 to 5 (may be random configuration) and z=1
to 10, or
[0135] (d) x=0, y=1 to 5 and z=1 to 10,
[0136] the compound has reduced polymerizability and as a result,
can have good storage stability and good handling as a
prepolymer.
[0137] In particular, in the case of (c) and (d), when an
oxypropylene group is introduced, the dielectric constant may be
lowered, however, due to the properties such that the melting point
and the viscosity do not increase even when the molecular weight is
high, the compound can be a very useful polymer depending upon the
intended application. Accordingly, by using properties of these
prepolymers and combining proper prepolymers or combining the
prepolymer with other polymers, a SPE suitable for a particular
application can be obtained.
[0138] When the ion conductive material for use in the ion
conductive laminate of the present invention contains a curable
substance, the curable substance is a substance capable of curing a
precursor substance (material) constituting Layer A, or converting
it into a more preferred ion conductive substance, by causing a
polymerization reaction or insolubilization reaction upon heating
and/or irradiating with active light. The curable substance is
added when the ion conductive material for use in the laminate of
the present invention is a so-called precursor substance
(material), namely, a material capable of being cured or converted
into a more preferred ion conductive substance resulting from
physical or chemical change caused by heating or irradiating with
active light. Examples of the curable substance include compounds
having an unsaturated double bond, compounds having a ring-opening
heterocyclic ring such as an epoxy structure or a glycidyl
structure, and compounds having a hydroxyl group, a thiol group, an
amino group, an isocyanate group or a condensing or polycondensing
group. Specific examples of these compounds include the
above-described functional monomers and oligomers. Layer A
containing a curable substance or a layer comprising a precursor
material of Layer A is heated and/or irradiated with active light
to polymerize, condense or polycondense the curable substance
itself, or to react the curable substance with other substances or
polymers present in the precursor substance to form a cross-linked
structure, thereby curing the precursor substance (material). As a
result, the material constituting Layer A has improved mechanical
strength or ion conductivity as compared with that of the precursor
substance.
[0139] In the ion conductive material constituting Layer A, the
content of the ion conductive substance such as the above-described
polymer varies depending upon the ionic substance such as an
electrolyte salt mixed therein or other components, or depending
upon the use of the laminate. However, if the content of the ion
conductive substance is too small, the strength of Layer A, namely,
the ion conductive material is too low and the shape stability of
Layer A in the laminate is poor. As a result, when the laminate is
used in an electrochemical element or electrochemical apparatus,
the element or the apparatus (device) is disadvantageously
deteriorated in performance or quality. On the other hand, if the
content of the ion conductive material is too large, the amount of
an ionic substance which can be contained therein or the content of
a solvent or other substances used in the mixing and/or compounding
is reduced to too great an extent. As a result, disadvantageously,
the number of ion carries may be deficient or the ion mobility may
be lowered to cause a decrease in the ion conductivity. Therefore,
the amount of the ion conductive substance in the ion conductive
material is preferably from 30 to 99.9 wt %, more preferably from
50 to 99 wt %, of the total amount of the ionic substance and the
ion conductive substance.
[0140] The addition amount of ion conductive material constituting
Layer A varies depending upon the ion conductive substance such as
a polymer, the ionic substance such as an electrolyte salt, or
other components used, or depending upon the use of the laminate.
Also, a solvent may be appropriately present therein. When the ion
conductive material for use in the ion conductive laminate of the
present invention contains a solvent, the solvent is a substance
contained in the ion conductive material which has a certain
melting point within the range of from 15 to 80.degree. C., or a
substance which is flowable within the above-described temperature
range and under a pressure of 1 kgf/cm.sup.2. The solvent may be
used to achieve good mixing or compounding of the ion conductive
material constituting Layer A of the laminate with other
substances. More specifically, the solvent may be used to achieve
uniform mixing or compounding with other substances constituting a
mixture or composite containing the ionic substance and the ion
conductive material, such as a curable substance, an additive or a
filler, or to improve the ion conductivity of the ion conductive
material constituting Layer A, or to control the curing reaction by
heating or irradiating the ion conductive material constituting
Layer A with active light, or to improve processability in
producing a laminate using the ion conductive material constituting
Layer A or properties of the laminate. The solvent may be
incorporated into the ion conductive material constituting Layer A
in an amount as needed. However, when Layer A of the laminate of
the present invention is a SPE or PGE containing a solvent, the
amount of the solvent is preferably small to the extent that the
solvent does not ooze out from Layer A. The solvent may be added to
Layer A so as to improve processability or usability in producing
or using the laminate of the present invention, or the solvent may
be added to improve processability of a precursor material
containing a precursor of the constituent material of Layer A, and
then Layer A may be laminated with Layer B, Layer C or the
above-described thin layer. Depending upon the kind of laminate,
this technique is particularly preferred. However, when Layer A of
the laminate is used substantially in the solid state, such as a
SPE or PGE, the amount of the solvent is preferably reduced before
use to the extent that the solvent does not ooze out from Layer
A.
[0141] The solvent for use in the present invention preferably has
good compatibility with an ion conductive substance such as an ion
conductive polymer constituting Layer A of the laminate, a large
dielectric constant of 1 or more, a boiling point of 70.degree. C.
or higher and a wide electrochemical stability, more preferably an
organic solvent. However, depending upon the kind or use of the
laminate, the ion conductivity may be improved when water is
present, and in this case, water may be used as a solvent. Examples
of the organic solvent include oligoethers such as triethylene
glycol dimethyl ether and tetraethylene glycol dimethyl ether,
carbonates such as ethylene carbonate, propylene carbonate,
dimethyl carbonate, diethyl carbonate, vinylene carbonate and
(meth)acryloyl carbonate, lactones such as .gamma.-butyrolactone,
aromatic nitriles such as benzonitrile and tolunitrile, sulfur- or
nitrogen-containing compounds such as dimethylformamide, dimethyl
sulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone and sulfolane,
phosphate esters, and alcohols such as ethanol, propanol and
butanol. Among these, preferred are oligoethers, carbonates and
lactones. The above-described solvent includes substances having a
function also as a non-polymerizable plasticizer for an ion
conductive material.
[0142] In general, as the content of the solvent is increased, the
ion conductivity of the SPE or PGE in Layer A increases. However,
when the solvent content is too large, the mechanical strength of
SPE or PGE may be reduced. Also, in general, as the content of the
solvent is increased, the viscosity of the ion conductive material
or a precursor material thereof in Layer A is reduced (or increased
in flowability). Accordingly, several advantages may be realized
such that Layer A is formed having a uniform thickness in the
production of a laminate or when the laminate is used, the outer
layer (Layer B, Layer C or the above-described thin layer) is
easily peeled off and removed. However, if the content of the
solvent is too large, depending upon the intended laminate, the
flowability of the ion conductive material or a precursor material
thereof constituting Layer A is increased to the extent that
problems may arise such that the uniform thickness of Layer A
cannot be maintained or the dimension of the laminate cannot be
kept constant. The presence or absence of the solvent or the
content of the solvent varies depending upon the kind or use of the
laminate of the present invention. However, in general, the content
of the solvent in the ion conductive material constituting Layer A
is suitably from 0.1 to 10,000 parts by weight, preferably from 1
to 1,000 parts by weight, more preferably from 5 to 500 parts by
weight, per 100 parts by weight of the total amount of the ionic
substance and the ion conductive substance. Furthermore, when the
above-described curable substance, for example, a polymerizable
compound such as vinylene carbonate, (meth)acryloyl carbonate or
N-vinylpyrrolidone is used as a solvent appropriately in
combination with a non-polymerizable solvent and copolymerized with
the above-described functional monomer or oligomer, the content of
the solvent can be increased and the ion conductivity can be
improved without lowering the mechanical strength. Thus, this
technique is preferred.
[0143] When the ion conductive material for use in the ion
conductive laminate of the present invention contains an additive,
the additive may include a curing aid such as an initiator, a
polymerization catalyst, a chain transfer agent, a curing rate
controller, an oxidizing agent, an antioxidant, a stabilizer or
others. Additives are freely added to achieve the desired
properties of Layer A or the ion conductive substance in Layer A of
the laminate of the present invention.
[0144] When the ion conductive material for use in the ion
conductive laminate of the present invention contains an additive,
the amount of the additive varies depending upon the ion conductive
substance such as a polymer, the ionic substance such as an
electrolyte salt or other components that are mixed therein, and
also varies depending upon the use of the laminate. However, for
example, the amount of additives in the ion conductive material if
present is suitably from 0.0001 to 30 parts by weight, preferably
from 0.001 to 10 parts by weight, per 100 parts by weight of the
total amount of the ionic substance and the ion conductive
substance.
[0145] When the ion conductive material for use in the ion
conductive laminate of the present invention contains a filler, the
filler is a substance that is filled in Layer A so as to achieve
full use of desired properties of Layer A or the ion conductive
substance in Layer A, to increase mechanical strength of Layer A,
to elevate the shape stability of Layer A, or to improve
processability of Layer A. Examples thereof include thermoplastic
resins, thermosetting resins, polymers having rubber elasticity and
other organic and inorganic substances, which are added to control
strength or flexibility of Layer A, to keep the thickness of Layer
A constant, or to improve shape stability. More specifically, for
example, in order to obtain a laminate comprising an ultrathin
Layer A having a constant thickness of from 1 to 10 .mu.m or
smaller, alumina particles, silica particles, latex particles or
non electron-conductive fine particles which do not inhibit ion
conduction and are stable in the ion conductive substance, having a
particle size corresponding to the thickness of Layer A, may be
used by incorporating these particles into Layer A in an amount
necessary for controlling the film thickness. Furthermore, in order
to obtain a laminate comprising Layer A having a constant
homogenous film thickness of from 1 to 1,000 .mu.m and having good
flexibility, excellent mechanical strength and processability,
polyethylene nonwoven fabric, polypropylene nonwoven fabric or
other porous non electron-conductive polymer matrix materials may
be used by incorporating the same into Layer A in an amount as
needed.
[0146] When the ion conductive material for use in the ion
conductive laminate of the present invention contains the
above-described filler, the amount of the filler may vary depending
upon the ion conductive substance such as an ion conductive
polymer, the ionic substance such as an electrolyte salt or other
components that are mixed therein, or may vary depending upon the
use of the laminate. However, the amount of filler in the ion
conductive material if present is suitably from 0.01 to 900 parts
by weight, preferably from 0.1 to 300 parts by weight, per 100
parts by weight of the total amount of the ionic substance and the
ion conductive substance.
[0147] The ion conductive material in the ion conductive laminate
of the present invention has a specific resistivity at room
temperature (20.degree. C.) of 10.sup.6 .OMEGA..multidot.cm or less
in order to provide various elements or electrically conductive
materials having excellent capability using the above-described ion
conductive substance. The specific resistivity at room temperature
is more preferably 10.sup.5 .OMEGA..multidot.cm or less when it is
used in electrochemical elements or apparatuses, and more
preferably 10.sup.4 .OMEGA..multidot.cm or less in order to produce
electrochemical elements or apparatuses having further higher
capability. The term "a non ion-conductive material" means a
material having an ion conductivity of 10.sup.-10 S/cm or less when
measured at 25.degree. C.) by a known AC impedance method (P. R.
Soerensen et al.; Electrochimica Acta, Vol. 27, No. 12, pages
1671-1675 (1982)).
[0148] In the ion conductive laminate of the present invention,
Layer B and Layer C each must have an ion conductivity lower than
that of Layer A so as to prevent or reduce as much as possible
aging change in conductivity, stability or mechanical properties of
the ion conductive material of Layer A. This may result from
penetration or diffusion of ionic species undertaking ion
conduction in Layer A into Layer B or Layer C in the laminate. In
the laminate of the present invention, the ion conductivity of each
of Layer B and Layer C is desirably one tenth ({fraction (1/10)})
or less, preferably one hundredth ({fraction (1/100)}) or less, and
more preferably one thousandth ({fraction (1/1,000)}) or less, than
the ion conductivity of Layer A.
[0149] When the ion conductive laminate of the present invention
has a thin layer(D.sub.1 or D.sub.2) comprising a metal, a metal
oxide or carbon between Layer B and layer A (or between Layer C and
Layer A), a Layer B/thin layer D.sub.1 (or Layer C/thin layer
D.sub.2) laminate in the state such that the ion conductivity is
lower than that of Layer A, may be provided on Layer A. More
specifically, when the thin layer (D.sub.1 or D.sub.2) has an ion
conductivity lower than that of Layer A, the ion conductivity of
Layer B located opposite Layer A through the thin layer D.sub.1 (or
Layer C located opposite Layer A through the thin layer D.sub.2)
itself may not necessarily be lower than that of Layer A. On the
contrary, when the thin layer (D.sub.1 or D.sub.2) has an ion
conductivity higher than that of Layer A, Layer B located opposite
Layer A through the thin layer D.sub.1 (or Layer C located opposite
Layer A through the thin layer or D.sub.2) itself may be sufficient
if it comprises a material having an ion conductivity lower than
that of Layer A. In this context, Layer B and Layer C may include
Layer B/thin layer D.sub.1 and Layer C/thin layer D.sub.2,
respectively, as far as the thin layer D.sub.1 and D.sub.2 has a
function in terms of ion conductivity to the extent that Layer B
and Layer C in the laminate of the present invention should have
been required to have, respectively, if the thin layer D.sub.1 and
D.sub.2 are not present.
[0150] A thin layer (D.sub.1 or D.sub.2) comprising a metal, a
metal oxide or carbon provided between Layer B and Layer A (or
between Layer C and Layer A) in the ion conductive laminate of the
present invention can solve handling or use problems, which may
result from the production, storage or use of the laminate
depending upon the kind of Layer A, Layer B or Layer C constituting
the laminate. Accordingly, the ion conductive material having a
thin layer (D.sub.1 or D.sub.2) comprising a metal, a metal oxide
or carbon provided between Layer B and Layer A (or between Layer C
and Layer A) is one preferred embodiment of the present invention.
The presence of the above-described thin layer is accompanied by
various advantageous effects. Namely, the thickness of Layer A can
be made homogenous in constructing the laminate, or the quality,
strength, storage stability or handling properties of Layer A may
be improved in various electrochemical elements or apparatuses
after peeling and without deforming the shape of Layer A upon use,
or in handling properties upon use in electrically conductive
materials, for example, for preventing electrification.
[0151] The constituent material of the thin layer is selected
depending on the kind of the laminate and its intended purpose.
Examples thereof include metals and alloys such as aluminum,
copper, gold, platinum, silver and stainless steel, metal oxides
such as indium tin oxide (ITO), alumina and silica, and carbon-base
substances such as graphite, diamond and impermeable carbon
materials.
[0152] In the laminate, when both of Layer B and Layer C are
electron conductive materials and when Layer B and Layer C are
placed into direct contact with each other or each is connected to
another electrically conductive material, for example, when the
laminate is bent, a plurality of laminates are piled, or the
laminate is connected to an electric conductor (either
intentionally or not), an electrical closed circuit is formed
between Layer B/Layer A/Layer C in the laminate or between
laminates. This causes an unexpected application of voltage to the
material constituting Layer A. As a result, a problem of aging
deterioration of the laminate tends to arise such that ions of
Layer A migrate or the ion conductive material is denatured.
Accordingly, at least one of Layer B and Layer C must be a non
electron-conductive material. The term "a non electron-conductive
material" as used herein means a material which is not
electron-conductive. Thus, a non electron-conductive material is
either an insulating material, or an ion conductive material having
no electron-conductive property. Examples of a material which is
electron-conductive is those such as metals, metal alloys,
metal-coated materials, electroconductive polymers and
electroconductive ceramics as described in U.S. Pat. No.
5,004,657.
[0153] In the ion conductive laminate of the present invention,
when Layer B, Layer C or a thin layer comprising a metal, a metal
oxide or carbon has good wettability to Layer A, the laminate can
be advantageous in that Layer B, Layer C or the above-described
thin layer is in good contact with Layer A. In particular, in
electrochemical apparatuses such as a battery or a capacitor, there
is a demand for thinner solid polymer electrolytes having improved
thickness accuracy. In this case, Layer B, Layer C or the
above-described thin layer having good wettability to Layer A is
preferably used. In general, the wettability is higher as the
contact angle of the objective liquid to the substrate surface is
smaller. Because Layer A of the laminate of the present invention
comprises a material which provides good mobility of ionic species
within the layer, polyethylene glycol having an average molecular
weight of 400 (Mw=380 to 420) was used as a model substance having
a polyalkylene oxide chain which is one of the representative
substance of materials constituting Layer A to determine the
contact angle thereof at 23.degree. C. to various materials used as
Layer B, Layer C or the thin layer by a liquid drop method
(automatic contact angle meter Model CA-Z, manufactured by Kyowa
Kaimen Kagaku KK). Thus, the contact angle, for example, is about
53.degree. to polypropylene (stretched film), about 46.degree. to
polyethylene, about 37.degree. to polyethylene terephthalate, about
28.degree. to nylon 6 (stretched film), about 20.degree. to
aluminum foil, about 15.degree. to alumina-evaporated polyethylene
terephthalate film (alumina surface) and about 8.degree. to
silica-evaporated polyethylene terephthalate film (silica surface).
When not wetted, the contact angle is obtuse (the contact angle of
mercury on glass is about 140.degree., for example). In the
laminate of the present invention, when Layer A is, for example, a
thin layer having a homogenous thickness of from 0.1 to 1,000 .mu.m
(for example, a thickness accuracy within .+-.30%), any of Layer B,
Layer C and the thin layer is preferably a layer comprising a
material having a contact angle (measured by the above-described
method) to polyethylene glycol of 80.degree. or less. When Layer A,
for example, is a thinner layer having a homogenous thickness (for
example, a thickness accuracy within .+-.20%), any of Layer B,
Layer C and the thin layer is more preferably a layer comprising a
material having a contact angle of 60.degree. or less. In
particular, when Layer A is a very thin layer having a homogenous
thickness of from 0.1 to 50 .mu.m, any of Layer B, Layer C and the
thin layer is particularly preferably a layer comprising a material
having a contact angle of 40.degree. or less.
[0154] When the laminate of the present invention is used for
integrating the ion conductive material constituting Layer A of the
ion conductive laminate of the present invention into
electrochemical apparatuses such as batteries, capacitors and
electrochromic displays, it is preferably used in the production of
apparatuses in such manner that at least one of Layer B and Layer C
of a laminate consisting of Layer B/Layer A/Layer C is removed by
peeling it off from Layer A. Or, in the case where the laminate has
a metal, metal oxide or carbon thin layer D.sub.1 (or D.sub.2)
between Layer B (or Layer C) and Layer A, the Layer B (or Layer
C)/the thin layer D.sub.1 (or D.sub.2) is removed by peeling it off
from Layer A. Layer A is then placed on an electrode, a separator,
an electric conductor or other substrate which is a constituent
material of the electrochemical apparatus such as a battery,
capacitor and electrochromic material. In this case, the adhesion
strength between Layer B and layer A, between Layer A and Layer C
or between the thin layer and Layer A is preferably low to the
extent that the structure or shape of Layer A is not deformed due
to the physical stress caused upon removal of Layer B, Layer C or
the thin layer laminated on Layer A by peeling or the like method.
Accordingly, when the laminate of the present invention is used
according to the above-described method, Layer A preferably has a
peel strength such that Layer B, Layer C or the thin layer can be
peeled off without substantially deforming the shape of Layer A. In
other words, Layer B, Layer C or the thin layer has good
releasability (peelability) to the extent that these layers can be
peeled off from Layer A without substantially deforming the shape
of Layer A.
[0155] In general, the releasability is considered to be better as
the wettability between the substrate and the layer to be peeled
off is lower, and accordingly, as the above-described contact angle
is larger. Also, in the present invention, electrochemical
apparatuses such as batteries and capacitors are very preferably
produced using, as Layer B or Layer C, polypropylene (stretched
film) or polyethylene having a large contact angle among the
above-described various materials. Polypropylene and polyethylene
also exhibit very good releasability from Layer A, by peel-removing
Layer B or Layer C from Layer A and then placing Layer A on an
electrode, a separator, an electric conductor or other substrate
which is a constituent material of the electrochemical
apparatus.
[0156] On the other hand, it has been found that a thin layer
comprising a metal such as aluminum, a metal oxide such as alumina
and silica, or carbon, which are considered to have poor
releasability due to a smaller contact angle based on the above
reasoning, can be unexpectedly peeled off and removed from Layer A
without causing any damage of the structure or shape of Layer A.
This depends upon the strength of electrolyte Layer A. For example,
in the case of Layer A having a tensile strength of 1 kg/cm.sup.2
or more, then Layer A can be used in the production of
electrochemical apparatuses.
[0157] The releasability has a reverse interrelationship with the
adhesive property which appears to be based on various factors at
the interface between a solid and a solid, and cannot be predicted
from the wettability alone based on the inter-molecular interaction
at the interface between a solid and a liquid as described above.
In first laminating Layer A, good wettability is important to
achieve homogenization of the surface at the lamination interface.
However, when Layer A contains a curable substance or a solvent,
Layer A is converted from a flowable material into a substantially
solid material after a curing reaction or removal of the solvent to
increase the strength of Layer A, or when layer A has from the
beginning a strength sufficiently high to endure the peeling, an
outer layer even having a small contact angle can be smoothly
peeled off. In practice, metals and metal oxides such as aluminum,
alumina and silica, having a contact angle smaller than that of
nylon 6 and polyethylene terephthalate exhibit not only good
wettability to Layer A but also good releasability from Layer A.
Hence, these materials are very preferably used in various
laminates of the present invention.
[0158] When the ion conductive laminate is used in the production
of various electrochemical elements or apparatuses or as an
electrically conductive material and the outer layers (Layer B or
Layer B/thin layer D.sub.1 and/or Layer C or thin layer
D.sub.2/Layer C) provided on the upper and lower parts of Layer A
are peeled off and removed before use, the releasability between
one outer layer to be peeled off and Layer A must be equal to or
greater than, preferably greater than, the releasability between
other outer layer and Layer A. Furthermore, when two outer layers
are peeled off in sequence before use at a desired step during the
production of the above-described elements or apparatuses, the
releasability between the outer layer to be peeled off first
(hereinafter referred to as the first release outer layer) and
Layer A must be equal to or greater than, preferably greater than,
the releasability between the outer layer to be peeled off
afterward (hereinafter referred to as the second release outer
layer) and Layer A.
[0159] For example, when a suitable combination of first release
outer layer and a second release outer layer is indicated as [
xx-YY], examples of the combination include
[polypropylene-alumina], [polypropylene-silica],
[polypropylene-aluminum], [polypropylene-PET],
[polyethylene-alumina], [polyethylene-silica],
[polyethylene-aluminum, [polyethylene-PET], [alumina-PET],
[silica-PET], [aluminum-PET], [polypropylene-corona
discharge-treated polyethylene], [alumina-nylon], [silica-nylon]
and [aluminum-nylon]. When the outer layer has the above-described
thin layer thereon, the releasability between Layer B/thin layer
D.sub.1 or thin layer D.sub.2/Layer C and Layer A is determined by
the releasability between the thin layer and Layer A. Accordingly,
although only the thin layer is indicated in the above-described
combination examples, the thin layer may be Layer B/thin layer
D.sub.1 or thin layer D.sub.2/Layer C.
[0160] As described in the foregoing, when at least one outer layer
(Layer B, layer C or the thin layer) is peeled off before use from
Layer A of a laminate of the present invention comprising layer A
having a homogenous thickness of from 0.1 to 1,000 .mu.m, the
contact angle range capable of achieving both the contact property
and the releasability which are generally considered to conflict
with each other, is preferably from 5 to 80.degree., more
preferably from 7 to 60.degree.. However, when the strength of
Layer A is higher than the peel strength of Layer B, Layer C or the
thin layer from Layer A, they can be peeled off without causing any
substantial damage to the shape of Layer A. Therefore, the contact
angle is not necessarily restricted to the above-described
preferred range.
[0161] The properties of the ion conductive material such as a SPE
and PGE for use in the laminate of the present invention are
readily changed, such as the ion conductivity due to water or a
polar molecule such as a polar solvent. Accordingly, in the ion
conductive laminate of the present invention, in order to prevent
aging change in conductivity, stability or mechanical properties of
the ion conductive material in Layer A resulting from invasion or
elution of liquid (a generic term inclusive of water and a solvent
component) such as water or a solvent component passed through
Layer B or Layer C to or from the ion conductive material such as a
SPE or PGE constituting Layer A, Layer B and Layer C or Layer B and
Layer C each having the above-described thin layer thereon are
preferably a liquid impermeable layer, more preferably a water
impermeable layer. The liquid impermeable layer or water
impermeable layer may be sufficient if it comprises a generally
well-known liquid impermeable or water impermeable material. When
the laminate of the present invention contains a solvent, the
liquid impermeable material is not particularly limited as long as
it is a liquid impermeable material having resistance against the
solvent. Examples thereof include polyolefins such as polyethylene
and polypropylene, polyethylene terephthalate, polybutylene
terephthalate, saturated polyesters produced from diol and
dicarboxylic acid, polycarbonate, polyacetal, polystyrene,
polyvinyl chloride, acrylic resin, polyacrylonitrile, ABS resin, AS
resin polyamide such as nylon 6 and nylon 6-6, polyphenylene oxide,
polyphenylene sulfide, polysulfone, polyethersulfone,
polyallylsulfone, polyarylate, polyimide, polyamideimide,
fluorocarbon resin, other thermoplastic resins, natural and
synthetic rubbers, aluminum, copper, stainless steel, other metals,
alloys, metal oxides, glass, phenolic resin, urea resin, melamin
resin, epoxy resin, unsaturated polyester resin, silicon resin,
thermosetting acrylic resin, diallylphthalate resin, other
thermosetting substances having two or more functional groups such
as a polymerizable unsaturated bond or a cyclic ring, and
thermosetting resin such as a cured product obtained by curing a
polymerizable mixture containing the above-described substance.
From these, a material suitable for the respective laminates may be
selected and used.
[0162] Among these substances for constituting Layer B or Layer C,
thermoplastic resin can be hot-melted and formed, for example, into
a plate, sheet or film having a desired thickness. Therefore, this
is practically advantageous in forming Layer B or layer C and is
very preferred. When Layer B or Layer C is previously processed
into an optional shape (structure) having a predetermined
dimension, for example, a plate, a disc, a sheet, or a box or
cylinder with a projection or a recession, having a predetermined
size and used as Layer B or Layer C constituting the laminate of
the present invention or used for a laminate having excellent
dimensional stability or strength, when the laminate is used at a
relatively high temperature or in an environment where the
temperature greatly changes, when the laminate is used in an
environment where a considerably strong mechanical stress is
applied from the outside, or when Layer B or Layer C is a structure
or a constituent part constituting an electrochemical element or
apparatus such as a battery, a capacitor or an electrochromic
element, which is produced using the laminate of the present
invention, so-called engineering plastics having excellent heat
resistance or mechanical properties are preferred among the
above-described thermoplastic resins. More specifically,
engineering plastics such as polyester, polycarbonate, polyacetal,
polyamide, polyphenylene oxide, polyphenylene sulfide, polysulfone,
polyethersulfone, polyallylsulfone, polyarylate, polyimide,
polyamideimide and fluorocarbon resins including
polytetrafluoroethylene (PTFE),
tetrafluoroethylene/hexafluoropropylene copolymer (FEP),
tetrafluoroethylene/perfluoroalkoxyethylene copolymer (PFA) and
polyvinylidene fluoride (PVdF) are appropriately used according to
the intended use. These thermoplastic resins may be either
stretched or unstretched. In addition, inorganic materials such as
glass and metal oxide, metals and thermosetting resins are very
preferably used. In particular, in order to produce a laminate
comprising Layer B or Layer C which comprises a non
electron-conductive material and is previously formed into a shape
having a predetermined dimension, or to produce a laminate
comprising Layer B or Layer C as a non electron-conductive layer
having excellent strength, engineering plastics and thermosetting
resins are particularly preferred. The engineering plastic which
can be suitably used as a material for forming Layer B or Layer C
in the laminate of the present invention is a plastic satisfying at
least three conditions out of four conditions, namely, (1) a
tensile strength of 5.5 kg/mm.sup.2 or more, (2) a tensile modulus
of elasticity of 200 kg/mm.sup.2 or more, (3) a heat distortion
temperature of 140.degree. C. or higher at 4.6 kg/cm.sup.2 and (4)
an Izod notched impact strength of 4 kg.multidot.cm/cm or more.
Examples of such an engineering plastic include engineering
plastics described above and those described in Ken Ihouchi, Fine
Polymer & Engineering Plastics, Kaisetsu to Bussei Hyo
(Description and Physical Properties Thereof), "Engineering Plastic
Gaisetsu (Introduction)", pages 175-184, Kagaku Kogyo Nippo Sha
(Sep. 30, 1978). However, the present invention is by no means
limited thereto.
[0163] In producing, using or storing the ion conductive laminate
of the present invention, when Layer B and Layer C both comprise a
material having a high dielectric constant, dielectric polarization
is readily generated in Layer B and Layer C due to an external
electric field. Accordingly, when an unexpected electric field is
applied from the outside of the laminate, an electrical double
layer or dielectric polarization may be generated at the interface
between Layer A, which comprises a SPE (or PGE) and is present
between Layer B and Layer C, and these outer layers and/or in Layer
A. As a result, depending upon the kind or use of the laminate, the
quality stability of Layer A may be adversely affected.
Accordingly, although this is not restricted only to the laminate
of the present invention, at least one of Layer B and Layer C
preferably has a low dielectric constant and the dielectric
constant (determined according to ASTM D-150; 10.sup.6 Hz) of the
layer having a lower dielectric constant is preferably 8 or less,
more preferably 6 or less. For example, the dielectric constants of
the various thermoplastic resins and thermosetting resins described
above are: from 2 to 3 for polyolefins such as polyethylene and
polypropylene, from 3 to 5 for polyethylene terephthalate, from 3
to 4 for polybutylene terephthalate, from 2.8 to 3.5 for
polycarbonate, from 3 to 4 for polyacetal, from 2 to 4 for
polystyrene, from 2 to 5 for polyvinyl chloride, from 2 to 3 for
acrylic resin, from 2 to 5 for polyacrylonitrile and ABS resin,
about 3 for AS resin, from 2 to 8 for nylon 6, approximately from 3
to 6 for nylon 6-6, from 2.5 to 3.5 for polyphenylene oxide, from 3
to 5 for polyphenylene sulfide, from 3 to 4 for polysulfone, from 3
to 4 for polyethersulfone, from 3 to 4 for polyarylate, from 3 to 4
for polyimide, from 3 to 4 for polyamideimide, from 2 to 3 for
PTFE, from 6 to 8 for PVdF, from 2 to 3 for silicone rubber and
silicone resin, from 4 to 6 for phenol resin, from 3 to 6 for epoxy
resin, from 3 to 6 for diallylphthalate resin and from 3 to 8 for
unsaturated polyester resin.
[0164] In the ion conductive laminate of the present invention,
when Layer A comprises a material containing a curable substance,
the laminate may be heated as is, or Layer A may be cured by
heating and/or irradiating with active light after removing by
peeling or the like at least one of Layer B and Layer C. Or, if the
above-described thin layer is formed thereon, at least one of Layer
B/thin layer D.sub.1 and Layer C/thin layer D.sub.2 are removed to
obtain Layer A comprising an ion conductive SPE or PGE. However, in
order to cure Layer A by heating and/or irradiating with active
light without removing by peeling or the like Layer B or Layer C
from the laminate to obtain Layer A comprising an ion conductive
SPE or PGE, at least one of Layer B and Layer C is preferably a
layer comprising a light transmissible material.
[0165] When the laminate of the present invention is a constituent
part of an electrochemical element or apparatus such as a
photoelectric cell, a solar cell or an electrochromic display, at
least one of Layer B and Layer C is also preferably a layer
comprising a light transmissible material. "Light transmissible"
means that the light transmissible layer of a laminate has a
transmissibility to active light having a specific wavelength (far
infrared light, near infrared light, visible light, ultraviolet
light, electron beam, .gamma. beam or X ray). The above-described
light passes through the light transmissible layer of the laminate
and reaches Layer A or the lower part thereof, or when the laminate
is used for a light-emitting element or coloring element, the
emission or coloration passes through the light transmissible layer
to reach the outside and the emission or coloration can be
confirmed from outside the laminate. The material constituting the
light transmissible layer may be selected from substances having
the above-described transmissibility to the objective active light,
among the various materials described above.
[0166] With respect to transmissibility to active light, the
transmission wavelength required varies depending upon the kind of
active light that is used. For example, in the case of a laminate
having, as a constituent element, Layer A containing the
above-described curable substance, when ultraviolet ray is used for
the curing, the transmittance at a wavelength of from 250 to 400 nm
is suitably 1% or more, more preferably 10% or more. When visible
light is used, the transmittance at a wavelength of from 400 to 740
nm is suitably 1% or more, more preferably 10% or more, and when
near infrared light is used, the transmittance at a wavelength of
from 740 to 1,500 nm is suitably 1% or more, more preferably 10% or
more. When electron beams are used, the wavelength of the electron
beams depends upon the electric field energy that is generated. The
wavelength can usually be expressed by: .LAMBDA.(nm)=(1.2)/(E
(eV)).sup.1/2, and the wavelength at 10 KeV is usually about 0.01
nm. Accordingly, although the kind of the material used is not
particularly limited, the transmission is facilitated if the
material is as thin as possible. The thickness is suitably 10 .mu.m
or less, preferably 1 .mu.m or less. The polymer is generally
sensitive to electron beams, and hydrocarbon-base polymers
containing no hetero atom are preferred. Polyolefins such as
polyethylene and polypropylene are more preferred as a cover film
(Layer B or Layer C).
[0167] On the other hand, consider the case where layer A of the
laminate of the present invention comprises a material that is not
stable to a specific active light, for example, where Layer A
contains a curable substance sensitive to active light. When Layer
A is cured after removing (by peeling or the like) Layer B or layer
C and then used, or if the above-described thin layer is formed
thereon, when Layer A is cured after removing at least one of Layer
B/thin layer D.sub.1 and Layer C/thin layer D.sub.2 and then used,
none of two outer layers selected from Layer B, Layer C, Layer
B/thin layer D.sub.1 and layer C/thin layer D.sub.2 are preferably
light transmissible. In this manner, the storage stability of the
laminate prior to use and the quality of the material constituting
layer A in the laminate can be maintained. The term "not
light-transmissible" to active light as used herein means that the
transmittance to an objective specific active light is suitably
less than 1%, more preferably 0.1% or less, still more preferably
0.01% or less.
[0168] In general, the transmittance is in inverse proportion to
the film thickness. Accordingly, even if the outer layer comprises
the same substance, the transmittance can be reduced to the
above-mentioned preferred range by increasing the film thickness.
Or, the outer layer may be rendered non light-transmissible by
appropriately blending therein known substances capable of
absorbing or reflecting the objective active light.
[0169] Furthermore, in order to maintain the quality of Layer A,
both of two outer layers of the laminate selected from Layer B,
Layer C, Layer B/thin layer D.sub.1 and Layer C/thin layer D.sub.2
are preferably gas impermeable. Thus, penetration of moisture, an
active gas such as oxygen, carbon dioxide, sulfur dioxide or
nitrogen oxide, or other gas molecules effecting the quality of
Layer A, which is present in the atmosphere where the laminate is
placed, can be prevented from passing through Layer B, Layer C or
the thin layer into Layer A.
[0170] For example, when Layer A of the laminate is an ion
conductive material containing the above-described curable
substance or a precursor material thereof, a curing reaction may
result upon heating and/or irradiating the laminate with active
light. Thus, it is important to prevent gases such as oxygen, which
inhibit initiation or progress of the curing reaction, from
penetrating into Layer A of the laminate.
[0171] With respect to the material constituting the gas
impermeable layer, known gas barrier resins, various thermoplastic
resins and thermosetting resins described above with respect to the
water impermeable or liquid impermeable material, known water
unabsorbable or water low absorptive resin may be used as the gas
impermeable outer layer of the laminate of the present invention.
Furthermore, the material may be selected from metals, alloys,
metal oxides, glass and carbon, which do not react with the gas and
are gas impermeable.
[0172] The water absorption and gas permeability of various resins
are described in many known publications. For example, Plastic
Dokuhon (Handbook), 18th rev., Plastic Age KK (1992) describes
various useful resins. For example, the water absorption (24 hr;
1/8") of various plastics are: from 0.3 to 0.5 for melamin resin,
from 0.1 to 0.2 for phenol resin (without filler), from 0.01 to 1.0
for unsaturated polyester (with glass fiber), from 0.4 to 0.8 for
urea resin, from 0.08 to 0.15 for epoxy resin, from 0.07 to 0.4 for
vinyl chloride resin (hard), from 0.5 to 1.0 for vinyl chloride
resin (soft), from 0.12 to 0.25 for polyacetal, from 0.3 to 0.4 for
methacrylic resin, from 2.0 to 4.5 for acetyl cellulose, 1.6 for
nylon 6 (polyamide), less than 0.01 for polyethylene, less than
0.01 for polypropylene, 0.00 for polytetrafluoroethylene, from 0.03
to 0.05 for polystyrene and 0.15 for polycarbonate. Furthermore,
the gas permeability (thickness: 25 .mu.m, 20.degree. C., 65% RH)
of various films to carbon dioxide, oxygen or nitrogen are:
[described in the order of CO.sub.2/O.sub.2/N.sub.2, unit:
cc/m.sup.2.multidot.atm.multidot.24 hr] [18,500/4,000/1,400] for
polyethylene (low density), [3,000/600/220] for polyethylene (high
density), [3,800/860/200] for polypropylene (unstretched),
[1,680/550/100] for polypropylene (biaxially stretched) (OPP),
[420/60/25] for polyester (polyethylene terephthalate), [253/60/16]
for nylon 6 (unstretched), [79/20/6] for nylon 6 (biaxially
stretched), [2,400/5,000/800] for polystyrene, [1,225/200/35] for
polycarbonate, [442/150/56] for polyvinyl chloride (hard),
[70/<115/2.2] for polyvinylidene chloride, [-/70/-] for MST
cellophane (vinyl chloride-base), [-/20/-] for K cellophane
(vinylidene chloride-base), [10/7/-] for polyvinyl alcohol, [-/2/-]
for ethylene-vinyl alcohol copolymer (EVOH) and [15/5 to 10/1.5]
for polyvinylidene chloride-coated OPP.
[0173] Among these resins, when the ion conductive material
constituting Layer A of the laminate of the present invention is
used for applications requiring extreme performance, polybutylene
terephthalate, polyethylene terephthalate, ethylene-vinyl alcohol
copolymer (EVOH), polycarbonate, polyamide (e.g., nylon 6),
polyacrylonitrile resin, which have a very low oxygen permeability,
stretched polypropylene, high-density polyethylene, polypropylene,
which have low permeability, and various other resins such as
polyethylene are preferred. In this regard, the front or back
surface is laminated with a gas barrier thin film against the
objective gas by a known method, or is subjected to surface
treatment to improve the gas barrier property. However, as long as
the performance requirements are satisfied, low-density
polyethylene or polystyrene inferior to the above-described resins
in gas barrier property, for example, against oxygen, may be used
depending upon the intended use of the laminate.
[0174] Of the various materials described above, materials having a
low moisture permeability are preferably used as a material
constituting Layer B or Layer C. This is because it is important to
prevent an increase in the water content of Layer A in view of
quality and use of the laminate of the present invention.
1TABLE 1 Moisture permeability of Various Resins Moisture
permeability (g/m.sup.2 .multidot. 24 hr) Resin (film) 40.degree.
C., 90% RH Polyethylene (low-density) 20 Polyethylene
(high-density) 10 Polypropylene (unstretched) 11 Polypropylene
(biaxially stretched) (OPP) 6 Polyethylene terephthalate 27 Nylon 6
(unstretched) 300 Nylon 6 (biaxially stretched) 145 Polystyrene 160
Polycarbonate 80 Polyvinyl chloride (hard) 40 Polyvinylidene
chloride 1.5 to 5 MST Cellophane (vinyl chloride-base) 50 K
Cellophane (vinylidene chloride-base) 10 Ethylene-vinyl alcohol
copolymer (EVOH) 50 Polyvinylidene chloride-coated OPP 4 to 5
[0175] Among the above-described thermoplastic resins, for example
the moisture permeability of various resin are known as shown in
Table 1 (see, Kogyo Zairyo (Industrial Materials), 39, [8], 38
(1990)). Layer B or Layer C of the laminate of the present
invention is more preferably a material selected from thermoplastic
resins, thermosetting resins, metals, alloys, metal oxides, glass
and carbon, and having a moisture permeability of 200
g/m.sup.2.multidot.24 hr (40.degree. C., 90% RH) or less, still
more preferably a material having a moisture permeability of 100
g/m.sup.2.multidot.24 hr or less.
[0176] When Layer B, Layer C or the thin layer as an outer layer of
the laminate of the present invention is a layer comprising an
electron conductive material and when the laminate is used in
producing an electrochemical element or apparatus or a constituent
part thereof, it is advantageous in view of the production process
of the element, apparatus or a constituent part thereof to use a
laminate where a lead wire or current collecting body comprising an
electron conductive electric conductor such as gold, platinum,
copper or stainless steel is connected to at least one of these
outer layers. A laminate where at least one of electron conductive
Layer B, Layer C and thin layer is connected to an electron
conductive electric conductor is a very preferred embodiment of the
laminate of the present invention.
[0177] It is also advantageous in view of the production process of
the above-described element or apparatus or a constituent part
thereof that the above-described laminate comprising at least one
outer layer connected to an electron conductive electric conductor,
which is one embodiment of the laminate comprising an outer layer
connected to an electron conductive electric conductor, is a
laminate where a lead wire or current collecting body comprising an
electron conductive electric conductor such as gold, platinum,
copper or stainless steel is connected to Layer A but is not in
contact with the above-described outer layer connected to an
electron conductive electric conductor. Thus, a laminate comprising
an outer layer and Layer A each connected to an electron conductive
electric conductor is a very preferred embodiment of the laminate
of the present invention.
[0178] Furthermore, when the laminate is used in the production of
an electrochemical element or apparatus or a constituent part
thereof comprising Layer A of the laminate of the present invention
as an electrolyte layer and any one of Layer B, Layer C or the
above-described thin layer as a constituent part, the use of a
laminate where a lead wire or current collecting body comprising an
electron conductive electric conductor such as gold, platinum
copper or stainless steel is previously connected to two different
sites of Layer A is advantageous in the production process of the
above-described element, apparatus or constituent part thereof.
Thus, a laminate where electron conductive electric conductors are
connected to two different sites of Layer A is a very preferred
embodiment of the laminate of the present invention. In this case,
two electron conductive electric conductors may be connected to
both sides of Layer A from a direction which is parallel to the
layer direction of the laminate, one electric conductor may be
connected from a direction which is parallel to the layer direction
and the other electric conductor may be connected by passing
through an outer layer of the laminate, two electric conductors
both may pass through either one of the upper and lower outer
layers of the laminate, or one electric conductor may pass through
from the upper portion and the other from the lower portion.
[0179] The thickness of Layer A comprising an ion conductive
material in the ion conductive laminate of the present invention
varies depending upon the intended application and is not
particularly limited. However, when Layer A is used in various
elements, apparatuses or electric conductor materials described
above, it is suitably from 0.1 to 1,000 .mu.m. In particular, when
Layer A is used in a thin electrochemical element or
electrochemical apparatus such as batteries, capacitors and
electrochromic elements, the thickness is preferably as small as
possible. For example, the thickness is more preferably from 0.1 to
300 .mu.m, still more preferably from 0.1 to 50 .mu.m. However,
depending upon the use, the thickness of Layer A may largely exceed
1,000 .mu.m.
[0180] The thicknesses of Layer B and Layer C of the laminate of
the present invention vary depending upon the intended application
and are not particularly limited. These thicknesses may be
appropriately determined according to the kind or intended use of
the laminate or depending upon the combination with Layer A. Even
in the case of a laminate where the thickness of Layer A is from
0.1 to 1,000 .mu.m, the thicknesses of Layer B and Layer C are not
particularly limited. However, the thicknesses of Layer B and Layer
C each is independently preferably, for example, from 1 to 5,000
.mu.m. When the laminate of the present invention is used in an
electrochemical apparatus or electric conductor material or in the
production thereof and when Layer B or Layer C is used to maintain
the mechanical strength, the thickness of Layer B or Layer C may
be, for example, several mm greatly exceeding 5,000 .mu.m. Of
course, Layer B, Layer C or the thin layer present between Layer B
or Layer C and Layer A may serve as an electrode of an
electrochemical element or an apparatus produced using the laminate
of the present invention.
[0181] When the laminate of the present invention comprises the
above-described thin layer between Layer A and Layer B and/or Layer
C, the thickness of the thin layer is not particularly limited and
can be appropriately selected according to the kind or intended use
of the laminate, or depending upon the combination with Layer A,
Layer B or Layer C before providing the thin layer in the laminate.
Even when the thin layer is present in the laminate where the
thickness of Layer A is from 0.1 to 1,000 .mu.m, the thickness of
the thin film layer is not particularly limited. However, it is
suitably from 50 to 5,000 .mu.m, preferably from 50 to 200
.mu.m.
[0182] The thickness of the laminate of the present invention is a
total of thicknesses of the respective layers depending upon the
intended use and may be determined according to the optional
selection of layers. It may range from several .mu.m to several mm,
or may exceed this range. Further, the size and the length of the
laminate can also be freely determined. The size may range from
several mm.sup.2 to several hundred mm.sup.2, or may exceed or fall
below this range. The length also may range from several mm to
several hundred mm, or may exceed or fall below this range.
[0183] FIGS. 1 to 8 each shows a schematical cross section of the
laminate of the present invention. Respective edge parts in the
direction parallel to the layer of the laminate of the present
invention may have any form according to the intended use of the
laminate. For example, Layer B (or Layer C) itself may be laminated
to cover the other outer layer, namely, layer C (or Layer B).
Furthermore, Layer B and Layer C may be the same layer, for
example, in a bag form; one edge, both edge parts or the peripheral
part of the laminate may be sealed with an optionally selected
sealant or adhesive which does not adversely affect the quality of
the laminate constructed, and comprises a material such as a
thermoplastic resin, rubber or thermosetting resin (e.g., epoxy
resin); or when the outer layers (Layer B and Layer C) each
comprises a thermoplastic resin, two outer layers may be bonded,
for example, by heat sealing, so as to lay one edge, both edge
parts or the peripheral part of the laminate in an unopen state,
which is preferred for achieving easy handling during the
production, use or storage of the laminate, particularly for
preventing direct contact of Layer A of the laminate with the outer
atmosphere. The laminate of the present invention includes, as a
laminate where a plurality of Layers A are laminated, for example,
a laminate where Layer B serves also as Layer C, a laminate
comprising a plurality of Layer B/Layer A laminates with Layer B
being laminated on Layer A (e.g., Layer B/Layer A/Layer B/Layer A
laminate) and a laminate comprising a plurality of laminates
consisting of Layer B/thin layer D.sub.1/Layer A wherein the
above-mentioned thin layer D.sub.1 is laminated on Layer A and
Layer B is laminated thereon (e.g., layer B/thin layer
D.sub.1/Layer A/Layer B/thin layer D.sub.1/Layer A laminate).
Furthermore, a rolled laminate obtained by rolling the
above-described laminate is also a laminate structure where Layers
A are laminated on two outer layers and included in the laminate of
the present invention. In this case, one edge or both edges (coiled
surface) of the roll is(are) preferably treated according to a
suitable method so as to provide a laminate where Layer A contained
in the laminate is placed in a state which is out of direct contact
with the outer atmosphere. Furthermore, even when the laminate has
a thin layer between Layer A and outer Layer B or outer Layer C,
one edge, both edge parts or the peripheral part of the laminate
is(are) preferably treated to be in an unopen state.
[0184] However, even when the laminate of the present invention is
in a form where the edge part is unclosed, if the laminate is
placed and handled in a closed container so as to keep the laminate
out of contact with an outer atmosphere or in an atmosphere which
does not adversely affect the laminate, particularly the quality of
Layer A, the edge part of the laminate need not be treated to be in
a closed state.
[0185] The water content of the ion conductive material
constituting Layer A of the ion conductive laminate of the present
invention varies depending upon the intended use and is not
particularly limited, however, in some uses, the water content is
preferably low. For example, when used in an electrochemical
element or apparatus such as a lithium battery, lithium ion
battery, non-aqueous electrical double layer capacitor or
non-aqueous electrochromic element, it is preferably 1,000 ppm or
less, more preferably 200 ppm or less.
[0186] The ion conductive laminate of the present invention can be
produced by various methods. A suitable method may be freely
selected according to the kind of the laminate to be produced. In
general, for example, the laminate of the present invention
described in any one of embodiments (1) to (26) above is produced
by (i) forming Layer A comprising an ion conductive material on
Layer B having an ion conductivity lower than that of Layer A in
such manner that the material of Layer A substantially does not
flow or move on Layer B to provide a laminate structure consisting
of Layer B/Layer A, (ii) laminating on Layer A Layer C comprising a
material having an ion conductivity lower than that of Layer A to
provide a laminate structure consisting of Layer B/Layer A/Layer C,
and then (iii) applying pressure to the laminate structure with a
force applied on the Layer B side surface of the laminate structure
and a force in opposition thereto applied on the Layer C side
surface of the laminate structure.
[0187] In the above step (i), the laminate structure consisting of
Layer B/Layer A may be formed by a method where Layer A is
previously shaped into a layer form such as a film or sheet and
then placed on Layer B, a method where Layer A is formed by
applying the ion conductive material constituting Layer A as it is
or after appropriately diluting the same with a solvent on Layer B
according to, for example, a spray method, a coating method, a
dipping method, a spin coating method or another optional method,
or a method where a layer comprising precursor materials of Layer A
is first formed by applying precursor materials of Layer A (for
example, a curable substance, additives, a solvent, or a material
containing a monomer or an oligomer or the like as a precursor of
the ion conductive polymer which is a precursor of the ion
conductive material) on Layer B according to a spray method, a
coating method, a dip method, a spin coating method or another
optional method and then the layer comprising the precursor
materials of Layer A is converted into the objective Layer A by
polymerization, curing or removal of solvent. In step (i), the
material of Layer A includes precursor materials of Layer A and "in
such manner that the material of Layer A substantially does not
flow or move on Layer B" includes not only the case where the
material of Layer A is substantially a solid material but also the
case where the material of Layer A is, even if it is a flowable
liquid, placed or being placed on Layer B in such manner that the
material substantially does not flow or move on Layer B. For
example, the liquid material of Layer A placed on Layer B
constituting a horizontal surface is in a state such that it does
not move or flow under gravity at least until it is processed in
the next step. More specifically, the case where the thickness of
Layer A comprising the material of Layer A is small to the extent
that it does not flow or move on Layer B constituting a horizontal
surface, comes under the above defined state. Also, the case where
the material of Layer A is, even if it is a flowable liquid (low
viscosity liquid) unable to maintain a desired thickness by itself,
poured, for example, into a frame spacer having a desired thickness
placed on Layer B to give Layer A the desired thickness, comes
under the above defined state.
[0188] In the above step (ii), Layer C is laminated on Layer A to
provide a laminate structure consisting of Layer B/Layer A/Layer C.
In this step, Layer C is laminated on Layer A of the laminate
structure consisting of Layer B/Layer A produced in step (i) as it
is or when the material of Layer A is a precursor material of the
ion conductive material for Layer A, after converting the layer
comprising the precursor material of Layer A by polymerization,
curing or removal of solvent into the objective Layer A. In
laminating Layer C, a method of previously shaping Layer C into a
layer form such as a film or sheet and then placing it on Layer A,
a method of applying the material constituting Layer C as it is or
after appropriately diluting it with a solvent on Layer A, for
example, by a spray method, a coating method, a dip method, a spin
coating method or another optional method to form Layer C on layer
A, or a method of applying a precursor material of Layer C (e.g.,
monomer, oligomer), for example, by a spray method, a coating
method, a dip method, a spin coating method or another optional
method to form a layer comprising the precursor material of Layer C
on Layer A and then converting the layer comprising the precursor
material of Layer C into the objective layer C by polymerization,
curing or removal of solvent to form a laminate structure
consisting of Layer B/Layer A/Layer C.
[0189] In the production of a laminate consisting of Layer B/Layer
A/Layer C of the present invention, in step (iii), the laminate
structure consisting of Layer B/Layer A/Layer C is pressed by
applying a force on the Layer B side surface of the laminate
structure and a force in opposition thereto on the Layer C side
surface so as to adjust the thickness of layers constituting the
laminate to a desired thickness or to achieve homogenization. The
pressure is applied after step (i) and step (ii) to press the
laminate structure consisting of layer B/Layer A/Layer C by
imposing a force on the Layer B side surface of the laminate
structure and a force in opposition thereto on the Layer C side
surface. In this case, any pressing method may be used. For
example, the laminate may be pressed according to a roller pressing
method by passing the laminate through nip rolls or other optional
pressure rolls, or according to a compression molding method where
presses having provided thereon, if desired, a spacer or die having
a desired thickness are pressed with a prescribed pressure on the
laminate from upside and downside such that the laminate is
interposed between spacers or within the mold. The pressing
pressure varies depending upon the kind of the laminate. However, a
pressure capable of performing laminate molding may usually be
used. A high pressure of from 50 to 300 kgf/cm.sup.2 that is used,
for example, in high-pressure laminating may be used depending on
the intended applicaton. However, in the case of the laminate of
the present invention, a pressure lower than the above-described
range, specifically a pressure of 50 kgf/cm.sup.2 or less as used
in so-called low-pressure laminating is preferred. In particular,
in producing a laminate which is placed into use after removing
outer layers from the laminate, as long as the pressure is of a
degree such that the thickness of Layer A of the laminate structure
consisting of Layer B/Layer A/Layer C can be homogenized, the
pressing pressure is preferably as low as possible in practice.
[0190] When the pressing as described above with respect to step
(iii) is performed simultaneously with step (i) or (ii), step (iii)
may be included in step (i) or (ii), and this technique is also
included in the above-described production method of the present
invention. More specifically, in step (i) and/or (ii), a layer to
be laminated or a layer comprising a precursor material thereof is
placed on another layer to provide a laminate structure or formed,
for example, by a spray method, a coating method, a dip method, a
spin coating method or another optional method to form a laminate
structure. Then, the laminate structure is pressed according to a
roller pressing method of passing the laminate through nip rolls or
other optional pressure rolls or according to a compression molding
method of pressing with a prescribed pressure from upside and
downside of the laminate structure with presses having provided
thereon, if desired, a spacer or a die having a desired thickness
such that the laminate is interposed between spacers or within the
die, thereby laminating respective layers of each laminate
structure formed. The pressure in pressing may be freely selected
as described in the above step (iii) depending upon the kind of the
laminate. However, when pressing is performed in step (i), it may
be performed under a pressure used in low-pressure laminating such
that the thickness of layer A of the laminate structure can be
homogenized and the pressure is preferably as low as possible in
practice. When pressing is performed in step (ii), the pressure may
vary depending upon the laminate. However, a pressure capable of
performing laminate molding is usually used. A high pressure of
from 50 to 300 kgf/cm.sup.2 that is used, for example, in the case
of high-pressure laminating may be used according to the intended
application. However, in the case of the laminate of the present
invention, a pressure lower than the above-described range,
specifically a pressure of 50 kgf/cm.sup.2 or less as used in
low-pressure laminating is preferred. In particular, in producing a
laminate which is used after removing outer layers from the
laminate, as long as the pressure is of a degree such that the
thickness of Layer A of the laminate structure consisting of Layer
B/Layer A/Layer C is homogenized, it is preferably as low as
possible in practice.
[0191] In the method of the present invention for producing a
laminate having a thin layer (D.sub.1 or D.sub.2) comprising a
metal, a metal oxide or carbon on at least one surface of Layer B
or Layer C, the thin layer (D.sub.1 or D.sub.2) is previously
formed on Layer B or Layer C by an optional method, and then Layer
B or Layer C having the thin layer (D.sub.1 or D.sub.2) may be
subjected to the above-mentioned steps (i), (ii) and (iii) to
produce the objective laminate.
[0192] In the method for previously laminating the thin layer
(D.sub.1 or D.sub.2) on Layer B or Layer C, lamination can be
performed by placing the thin layer which is previously formed on
Layer B or Layer C and, if desired, by roller pressing or
compression pressing the layers. Or, on Layer B or Layer C, a layer
comprising a material constituting the thin layer or a precursor
material of the thin layer is formed, for example, by a spray
method, a coating method, a dip method, a spin coating method, an
evaporation (vapor deposition) method or another optional method to
provide layer B or Layer C having laminated thereon the thin layer,
or a layer comprising a precursor material of the thin layer is
converted into the objective thin layer by polymerization, curing
or removal of solvent to thereby form Layer B or Layer C having
laminated thereon the thin layer (D.sub.1 or D.sub.2).
[0193] Furthermore, before laminating Layer C on Layer A in the
above-mentioned step (ii), the thin layer which is previously
formed may be laminated on Layer A, and Layer C is laminated
thereon to produce a laminate of the present invention having the
thin layer (D.sub.1 or D.sub.2) between Layer C and Layer A.
[0194] In the above-described methods, when a layer comprising a
precursor material containing a curable substance for forming Layer
A is converted into Layer A, the layer comprising a precursor
material of Layer A may be cured by heating and/or irradiating with
active light after step (i) to convert the layer into Layer A, and
then Layer C is laminated on Layer A to provide a laminate
structure consisting of Layer B/Layer A/Layer C. Or, a laminate
structure consisting of Layer B/Layer A precursor material
layer/Layer C may be formed through steps (i) and (ii), and then
the layer comprising the precursor material of Layer A may be cured
by heating and/or irradiating with active light to convert the
layer into Layer A to thereby provide a laminate structure
consisting of Layer B/Layer A/Layer C. Alternatively, the layer
comprising a precursor material of Layer A may be cured in the same
manner as described above at the pressurization step (iii) after
steps (i) and (ii) to convert the layer into Layer A.
[0195] In the above-described methods, when Layer B, Layer C or a
layer for forming the thin layer, comprising a precursor material
for forming Layer B, Layer C or the thin layer, is converted into
the objective Layer B, Layer C or the thin layer, the layer
comprising the precursor material may be cured by heating and/or
irradiating with active light after step (i), and/or steps (i) and
(ii) to convert the layer into the objective layer.
[0196] In this case, the curing may be performed by polymerizing
the curable substance by heating and/or irradiating with active
light. The polymerization may be performed by a general method
using polymerizability of the polymerizable functional group of the
polymerizable compound in the curable material. For example, a
general method using polymerizability of an acryloyl group or the
methacryloyl group in a polymerizable compound having an acryloyl
group or a methacryloyl group may be used. More specifically, the
polymerizable compound or a mixture of the polymerizable compound
with other polymerizable compounds capable of copolymerization
described above may be subjected to radical polymerization by
heating or irradiating with active light, cationic polymerization
or anionic polymerization, using a radical thermal polymerization
initiator such as azobisisobutyronitrile and benzoyl peroxide, a
radial photopolymerization initiator such as benzyl methyl ketal
and benzophenone, a cationic polymerization catalyst such as a
protonic acid (e.g., CF.sub.3COOH) and a Lewis acid (e.g.,
BF.sub.3, AlCl.sub.3), or an anionic polymerization catalyst such
as butyl lithium, sodium naphthalene and lithium alkoxide.
[0197] In the above-described production method, when Layer A is
Layer A comprising an ion conductive material containing a solvent
or a layer comprising a precursor material of Layer A containing a
solvent, the laminate may also be produced through the
above-mentioned steps (i), (ii) and (iii). A laminate structure
consisting of Layer B/Layer A having a solid or substantially solid
Layer A as a constituent layer may be produced by removing, if
necessary, a desired amount of solvent from Layer A or the layer
comprising a precursor material of Layer A, or a laminate
containing a considerable amount of solvent capable of various uses
may also be produced.
[0198] The laminate described in any one of embodiments (1) to (29)
above of the present invention may also be produced by the
following method which is a practical embodiment of the
above-described method. A Layer A/Layer C laminate or Layer B/Layer
A laminate is produced through a step of removing at least one of
Layer B and Layer C from Layer A of the laminate described in any
one of embodiments (1) to (29) or a step of removing Layer B or
Layer C having on the surface thereof facing Layer A a thin layer
comprising a metal, a metal oxide or carbon, together with the thin
layer from Layer A, to produce a Layer A/Layer C or Layer B/Layer A
laminate, and a step of laminating the laminate produced above on a
Layer A/Layer C or Layer B/Layer A laminate produced in the same
manner such that Layers A of respective laminates are bonded
together, to provide a Layer B/Layer A/Layer C, Layer B/Layer
A/Layer B or Layer C/Layer A/Layer C laminate structure as a new
laminate. Or, in the same manner, various electrochemical elements
or apparatuses having a Layer B/Layer A/Layer C, Layer B/Layer
A/Layer B or Layer C/Layer A/Layer C laminate structure can be
produced.
[0199] The ion conductive laminate of the present invention is
suitably used in various batteries, capacitors, electrochromic
elements, apparatuses thereof and other electrochemical elements
and apparatuses. In this case, it is advantageous to use Layer A,
which becomes a surface layer after removing at least one of Layer
B and Layer C from Layer A of the laminate of the present invention
described in any one of embodiments (1) to (29) above or after
removing Layer B or Layer C having on the surface thereof facing
Layer A a thin layer (D.sub.1 or D.sub.2) comprising a metal, a
metal oxide or carbon, together with the thin layer (D.sub.1 or
D.sub.2) from Layer A, in the production of the above-described
electrochemical elements and apparatuses. An electrochemical
element or apparatus can be produced through a step of forming a
layer comprising a material containing, for example, when a battery
is constructed, an electrochemically active substance (positive
and/or negative electroactive substance), on at least one removal
surface of Layer A as the surface layer.
[0200] According to the above-described method, batteries,
capacitors, electrochemical power generating elements and
apparatuses such as a photoelectric cell and a solar cell,
electrochemical coloring elements and apparatuses such as an
electrochromic element and apparatus, and electrochemical
light-emitting elements and apparatuses using an
electro-lumnescence material can be produced.
[0201] One example of the method for producing a secondary battery
using the laminate of the present invention is described in detail
below.
[0202] When a battery is produced using the ion conductive laminate
of the present invention, the battery preferably has a construction
such that the negative electrode comprises an electroactive
substance (negative electroactive substance) using as a carrier an
alkali metal ion such as an alkali metal, an alkali metal alloy or
a carbon material. Also, the negative electroactive substance has a
low oxidation-reduction potential such that a battery of high
voltage and high capacity can be obtained. Among these
electroactive substances, especially preferred are lithium metal
and lithium alloys such as a lithium/aluminum alloy, a lithium/lead
alloy and a lithium/antimony alloy because of their low
oxidation-reduction potential. The carbon material is also
especially preferred in that when it occludes Li ions, a low
oxidation-reduction potential is provided and moreover, the
material is stable and safe. Examples of the carbon material
capable of occluding and releasing Li ions include natural
graphite, artificial graphite, vapor phase process graphite,
petroleum coke, coal coke, pitch-base carbon, polyacene and
furalenes such as C.sub.60 and C.sub.70.
[0203] The positive electrode preferably comprises an electroactive
substance (positive electroactive substance) having a high
oxidation-reduction potential such as a metal oxide, a metal
sulfide, an electroconductive polymer or a carbon material, so that
a battery of high voltage and high capacity can be obtained. Among
these electroactive substances, preferred in view of high filling
density and high volume capacity density are metal oxides such as
cobalt oxide, manganese oxide, vanadium oxide, nickel oxide and
molybdenum oxide, and metal sulfides such as molybdenum sulfide,
titanium sulfide and vanadium sulfide, and particularly preferred
in view of high capacity and high voltage are manganese oxide,
nickel oxide and cobalt oxide.
[0204] The production method of these metal oxides and metal
sulfides is not particularly limited. They may be produced, for
example, by a general electrolytic or heating process as described
in Denkikagaku (Electrochemistry), Vol. 22, page 574 (1954). When
they are used in a lithium battery as an electroactive substance,
in the production of the battery, the substance is preferably used
in a state such that a Li element is inserted (compounded) into a
metal oxide or a metal sulfide, for example, in the form of
Li.sub.xCoO.sub.2 or Li.sub.xMnO.sub.2. The insertion method of the
Li element is not particularly limited and for example, a method of
electrochemically inserting Li ions or a method of mixing a salt
such as Li.sub.2CO.sub.3 with a metal oxide and subjecting the
mixture to heat treatment as described in U.S. Pat. No. 4,357,215
may be used.
[0205] In view of flexibility and easy formability into a thin
film, electroconductive polymers are preferred as the positive
electrode material. Examples of the electroconductive polymer
include polyaniline, polyacetylene and a derivative thereof,
polyparaphenylene and a derivative thereof, polypyrrolylene and a
derivative thereof, polythienylene and a derivative thereof,
polypyridinediyl and a derivative thereof, polyisothianaphthenylene
and a derivative thereof, polyfurylene and a derivative thereof,
polyselenophene and a derivative thereof, and polyarylene vinylene
and a derivative thereof such as polyparaphenylene vinylene,
polythienylene vinylene, polyfurylene vinylene, polynaphthenylene
vinylene, polyselenophene vinylene and polypyridinediyl vinylene.
Among these, especially preferred are polymers of an aniline
derivative soluble in an organic solvent. The above-described
electroconductive polymers for use as an electroactive substance in
a battery or in an electrode can be produced according to a
chemical, electrochemical or other known method.
[0206] With respect to other organic materials, disulfide compounds
such as 2,5-dimercapto-1,3,4-thiadiazole and mixtures of the
compound with an electroconductive polymer are preferred because of
their high capacity.
[0207] Examples of the carbon material include natural graphite,
artificial graphite, vapor phase process graphite, petroleum coke,
coal coke, fluorinated graphite, pitch-base carbon and
polyacene.
[0208] Also, the carbon material for use as an electroactive
substance in the battery or electrode of the present invention may
be a commercially available product or may be produced according to
a known method.
[0209] When the laminate of the present invention is used in the
production of a battery, the kind of electrolyte salt as an ionic
substance contained in the ion conductive material (SPE or PGE)
constituting Layer A and used for compounding the material is not
particularly limited and any electrolyte salts containing an ion
intended to be a charge carrier may be used. However, those having
a large dissociation constant in a SPE or PGE are preferred.
Specifically, alkali metal salts, quaternary ammonium salts such as
(CH.sub.3).sub.4NBF.sub.4, quaternary phosphonium salts such as
(CH.sub.3).sub.4PBF.sub.4, transition metal salts such as
AgClO.sub.4, and protonic acids such as hydrochloric acid,
perchloric acid and borofluoric acid are preferred.
[0210] The negative electroactive substance for use in the battery
of the present invention, as described above, preferably uses as a
carrier an alkali metal ion such as an alkali metal, an alkali
metal alloy or a carbon material and has a low oxidation-reduction
potential, so that a battery of high voltage and high capacity can
be obtained. Accordingly, the electrolyte in the SPE or PGE for use
in a battery using the above-described negative electrode with an
alkali metal ion as a carrier is preferably an alkali metal salt.
Examples of the alkali metal salt include LiCF.sub.3SO.sub.3,
LiPF.sub.6, LiClO.sub.4, LiI, LiBF.sub.4, LiSCN, LiAsF.sub.6,
LiN(CF.sub.3SO.sub.2).sub.2, NaCF.sub.3SO.sub.3, NaPF.sub.6,
NaClO.sub.4, NaI, NaBF.sub.4, NaAsF.sub.6, KCF.sub.3SO.sub.3,
KPF.sub.6 and KI. Among these, lithium or a lithium alloy is most
preferably used as the alkali metal because of high voltage, high
capacity and potential reduction of the film thickness. In the case
of a carbon material negative electrode, not only alkali metal ions
but also quaternary ammonium salts, quaternary phosphonium salts,
transition metal salts and various protonic acids can be used.
[0211] The mixing amount of the electrolyte salt varies depending
upon the polymer or other components of the ion conductive material
that are mixed. However, if the mixing amount is too small, the
number of ion carriers is deficient, whereas if it is too large,
the mobility is lowered to reduce the ion conductivity.
Accordingly, the mixing amount of the electrolyte salt in the ion
conductive material is preferably from 0.1 to 70 wt %, more
preferably from 1 to 50 wt %.
[0212] In the SPE of PGE as one preferred embodiment of the ion
conductive material of the laminate of the present invention, an
ion conductive material having added thereto an organic compound or
a slight amount of water is preferably used as a solvent for the
electrolyte, so that the ion conductivity can be further improved.
Preferred examples of the solvent which can be used include, among
the above-described solvents for use in the ion conductive
material, compounds having good compatibility with the polymer used
in the SPE or PGE constituting the ion conductive material, and
having a large dielectric constant of 1 or more, a boiling point of
70.degree. C. or higher and a wide electrochemical stability range.
Accordingly, specific organic solvents are more suitable than
water. Examples of the organic solvent include oligoethers such as
triethylene glycol dimethyl ether and tetraethylene glycol dimethyl
ether, carbonates such as ethylene carbonate, propylene carbonate,
dimethyl carbonate, diethyl carbonate, vinylene carbonate and
(meth)acryloyl carbonate, lactones such as .gamma.-butyroactone,
aromatic nitrites such as benzonitrile and tolunitrile, sulfur- or
nitrogen-containing compounds such as dimethylformamide, dimethyl
sulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone and sulfolane,
phosphate esters, and alcohols such as ethanol, propanol and
butanol. Among these, preferred are oligoethers, carbonates and
lactones. The solvent includes substances which function also as a
non-polymerizable plasticizer of the ion conductive material.
[0213] As the addition amount of the solution is increased, the ion
conductivity of the SPE or PGE increases. However, if the addition
amount is too large, the mechanical strength of the SPE or PGE is
reduced. The addition amount is preferably 10 times or less the
weight of the polymer used in the SPE or PGE. The solvent which is
a polymerizable compound such as vinylene carbonate, (meth)acryloyl
carbonate and N-vinyl pyrrolidone is preferably used in combination
with an appropriate amount of a non-polymerizable plasticizer to
copolymerize with the above-described functional monomer or
oligomer, thereby increasing the addition amount of the plasticizer
and improving the ion conductivity without causing any reduction in
mechanical strength.
[0214] In the production method of a battery using the laminate of
the present invention, at least one electrode is an electrode
containing the above-described electroactive substance and another
electrode is an electrode containing the above-described other
electroactive substance produced in the same manner or a commonly
used electrode. First, at least one of Layer B and Layer C of the
laminate of the present invention is peeled off from Layer A. Or,
Layer B or Layer C having on the surface thereof facing Layer A a
thin layer (D.sub.1 or D.sub.2) comprising a metal, a metal oxide
or carbon, is peeled off together with the thin layer from Layer A.
In the following, for the sake of convenience of description, a
production method of a battery where Layer B/thin layer
D.sub.1/Layer A/Layer C is used as a laminate and Layer B/thin
layer D.sub.1/Layer A obtained by removing Layer C is used in
laminating an electrode, is described. However, the laminate is by
no means limited to this structure and the outer layer that is
removed by peeling is not limited to Layer C. On the Layer A
surface of Layer B/thin layer D.sub.1/Layer A obtained in the
above-described step, namely, on the Layer A surface from which
Layer C laminated thereto is removed, one electrode processed into
a predetermined shape such as a film, sheet or disc is placed and
if desired, bonded under pressure to produce a laminate structure
consisting of Layer B/thin layer D.sub.1/Layer A/electrode (the
term "is placed on the Layer A surface" as used herein is not
limited to that a spacial position relationship that is vertical
but the relationship may also be inverse or horizontal). In forming
a laminate structure consisting of Layer B/thin layer D.sub.1/Layer
A/electrode, a pressure is preferably applied, if desired, to
ensure good contact between the electrode and Layer A. In this
case, Layer A most preferably contains a curable substance, or a
curable substance capable of being an ion conductive substance
after curing or a solution thereof is previously applied, for
example, by coating onto the surface of the electrode to be placed
on the Layer A surface, to form a thin coating. Then, Layer A
containing and/or not containing a curable substance is placed
thereon. In this case, after the electrode is placed on the Layer A
surface, during and/or after the application of pressure, heating
and/or irradiating with the above-mentioned active light is carried
out to obtain a laminate structure having very good adhesion
between the electrode and Layer A.
[0215] In laminating an electrode on Layer A, a spacer frame having
a predetermined thickness and formed of an insulating material may
be placed on the electrode. A laminate structure consisting of
Layer B/thin layer D.sub.1/Layer A produced from the laminate
(Layer B/thin layer D.sub.1/Layer A/Layer C) of the present
invention previously processed, for example, by cutting, into a
size matching the frame shape and size or a laminate structure
consisting of Layer B/thin layer D.sub.1/Layer A previously
processed, for example, by cutting, into a size matching the frame
size, may be placed within the spacer frame on the electrode, to
form a laminate structure with a spacer consisting of Layer B/thin
layer D.sub.1/Layer A/electrode.
[0216] Then, Layer B/thin layer D.sub.1 of the laminate structure
consisting of Layer B/thin layer D.sub.1/Layer A/electrode is
removed, for example, by peeling. On the Layer A surface of the
laminate structure consisting of Layer A/electrode thus obtained,
the other electrode which is processed in the same manner into a
predetermined shape and size such as a film, sheet or disc, as the
electrode already laminated, is placed and then, if desired, bonded
under pressure to produce a laminate structure consisting of
electrode/Layer A/electrode (also in this case, the term "is placed
on the Layer A surface" is not limited to a spacial position
relationship that is vertical but the relationship may also be
inverse or horizontal). In forming a laminate structure consisting
of electrode/Layer A/electrode, a pressure is preferably applied,
if desired, to ensure good contact between the electrode and Layer
A. In this case, Layer A most preferably contains a curable
substance, or a curable substance capable of being an ion
conductive substance after curing or a solution thereof is
previously applied, for example, by coating to the surface of the
electrode to be placed on the Layer A surface, to form a thin
coating. Then, Layer A containing and/or not containing a curable
substance is placed thereon. In this case, after the electrode is
placed on the Layer A surface, heating and/or irradiating with
active light is performed during and/or after the application of
pressure to obtain a laminate structure having very good adhesion
between the electrode and Layer A.
[0217] Examples of the active light include ultraviolet light,
visible light, near infrared light, far infrared light, an electron
beam, a .gamma. beam and X rays. An appropriate light may be used
in combination with a curable substance or an initiator.
[0218] Each electrode of the laminate consisting of electrode/Layer
A/electrode produced as described above is connected, if desired,
to a current collecting body. After placing the laminate in a
structure constituting a battery or when the current collecting
body also serves as a structure constituting the battery as such,
the structure is subjected to known processing, for example,
sealing of an open edge part with an insulating sealant such as an
epoxy resin or polyolefin resin, to obtain a battery.
[0219] In the production method of a battery of the present
invention, the above-described current collecting body may be
previously connected to the electrode at any step before production
of a laminate consisting of electrode/Layer A/electrode.
[0220] According to the production method of a battery using the
ion conductive laminate of the present invention, a high-quality
secondary battery using a whole solid type SPE or PGE having a
homogenous thickness, such as a lithium secondary battery and a
lithium ion secondary battery, can be produced. In particular, by
using the ion conductive laminate of the present invention in the
production of a battery, a thin secondary battery can be produced
which has a very thin layer comprising a SPE or PGE having a
homogenous thickness in good contact with the electrode.
Accordingly, the resulting battery has excellent electrical
properties, namely, a rapid charge/discharge property, high
coulombic efficiency and cyclability.
[0221] FIG. 9 shows a schematic cross section of one example of a
thin film solid secondary battery as one example of the battery of
the present invention produced as described above. In FIG. 9, the
numeral 1 is a positive electrode, 2 is a SPE or PGE, 3 is a
negative electrode, 4 is a current collecting body, 5 is an
insulating spacer and 6 is an insulating resin sealant.
[0222] Using the ion conductive laminate of the present invention,
a roll-type battery can also be produced. A laminate consisting of
positive electrode/Layer A/thin layer D.sub.1/Layer B and a
laminate consisting of negative electrode/Layer A/thin layer
D.sub.1/Layer B is produced by the same method as described above,
thin layer D.sub.1/Layer B is peeled from the respective laminates
and, for example, a film-type laminate consisting of positive
electrode/Layer A/negative electrode/Layer A or negative
electrode/Layer A/positive electrode/Layer A is produced in the
same manner as described above. A lead wire is connected to each
electrode, the resulting film laminate is rolled into a desired
roll, and the roll is inserted into a structure constituting a
battery and sealed according to a known sealing method to obtain a
roll-type battery. After inserting the roll into the structure
constituting a battery, for example, a curable substance used in
constructing an ion conductive substance constituting Layer A, a
SPE or PGE, or a mixture thereof, may be injected and polymerized.
The structure may then be sealed according to a known method to
obtain a roll-type battery.
[0223] An example of the production method of a solid electrical
double layer capacitor using the ion conductive laminate of the
present invention is described in detail below.
[0224] The kind of ionic substance used in Layer A comprising an
ionic conductive material of the present invention and present in
the SPE or PGE of a solid electrical double layer capacitor thus
produced is not particularly limited and compounds containing an
ion intended to be a charge carrier may be used. However, the
compound preferably has a large dissociation constant in a SPE or
PGE and contains ions which readily form a polarizable electrode
and an electrical double layer. Examples of such a compound include
quaternary ammonium salts such as (CH.sub.3).sub.4NBF.sub.4 and
(CH.sub.3CH.sub.2).sub.4NClO.sub.4, transition metal salts such as
AgClO.sub.4, quaternary phosphonium salts such as
(CH.sub.3).sub.4PBF.sub.4, alkali metal salts such as
LiCF.sub.3SO.sub.3, LiPF.sub.6, LiClO.sub.4, LiI, LiBF.sub.4,
LiSCN, LiAsF.sub.6, LiN(CF.sub.3SO.sub.2).sub.2,
NaCF.sub.3SO.sub.3, NaPF.sub.6, NaClO.sub.4, NaI, NaBF.sub.4,
NaAsF.sub.6, KCF.sub.3SO.sub.3, KPF.sub.6 and KI, organic acids
such as p-toluenesulfonic acid and salts thereof, and inorganic
acids such as hydrochloric acid and sulfuric acid. Among these,
quaternary ammonium salts, quaternary phosphonium salts and alkali
metal salts are preferred because they are capable of providing
high output voltage and a large dissociation constant. Among
quaternary ammonium salts, preferred are those having different
substituents on the nitrogen of the ammonium ion such as
(CH.sub.3CH.sub.2)(CH.sub.3CH.sub.2C-
H.sub.2CH.sub.2).sub.3NBF.sub.4 because of their high solubility
and large dissociation constant in the SPE or PGE.
[0225] With respect to the solid electrical double layer capacitor
produced using the ion conductive laminate of the present
invention, by using SPE or PGE comprising the ion conductive
material and having a homogenized thickness, a whole solid
electrical double layer capacitor having a high output voltage, a
large takeout current and excellent processability and reliability
can be provided.
[0226] FIG. 10 shows a schematic cross section of one example of
the solid electrical double layer capacitor of the present
invention. The numeral 4 is a current collecting body, a pair of
polarizable electrodes 7 are disposed inside the current collecting
body and SPE or PGE 2 is disposed therebetween. The numeral 5 is an
insulating spacer, and in this example, an insulating film is used.
The numeral 6 is an insulating resin sealant and 8 is a lead
wire.
[0227] The current collecting body 4 preferably uses a material
which is electron conductive and electrochemically anticorrosive
and has a specific surface area that is as large as possible.
Examples thereof include various metals, a sintered body thereof,
electron conductive polymers and carbon sheet.
[0228] The polarizable electrode 7 may be an electrode comprising a
polarizable material such as a carbon material usually used in an
electrical double layer capacitor. However, a carbon material
compounded with the ion conductive material constituting Layer A of
the ion conductive laminate of the present invention or a precursor
material thereof is preferred. The carbon material as a polarizable
material is not particularly limited as long as it has a large
specific area, however, carbon materials having a larger specific
area are preferred because the electrical double layer can have a
larger capacity. Examples thereof include carbon blacks such as
furnace black, thermal black (including acetylene black) and
channel black, activated carbons such as coconut husk carbon,
natural graphite, artificial graphite, so-called pyrolytic graphite
produced by a vapor phase process, polyacene, C.sub.60 and
C.sub.70.
[0229] In producing a polarizable electrode comprising a
polarizable material such as a carbon material and a polymer
obtainable from at least one curable substance (polymerizable
monomer) and/or a copolymer containing the compound as a copolymer
component, which is preferably used in the solid electrical double
layer capacitor, first, for example, at least one compound having a
structure substituted by the unit represented by formula (1) and if
desired, other polymerizable compounds and/or a solvent are added
to and mixed with a polarizable material. In this case, the mixing
ratio of each component is appropriately determined according to
the objective capacitor. The resulting polymerizable
monomer/polarizable material mixture is formed into a film on a
substrate, for example, on a current collecting body and then
polymerized by the same heating and/or irradiating with active
light as described above to produce a polarizable electrode.
According to this method, a composite thin film electrode in good
contact with the current collecting body can be produced.
[0230] Using two sheets of polarizable electrodes produced as
described above and according to the same method as the
above-described production method of a battery, a laminate
structure consisting of polarizable electrode/Layer A/polarizable
electrode is produced. Also in this case, the polarizable
electrode, the laminate of the present invention or the laminate
structure after removal of one outer layer may be previously
processed into a desired size or shape and then used in the
production of a laminate structure consisting of polarizable
electrode/Layer A/polarizable electrode.
[0231] Each electrode of the thus-produced laminate consisting of
electrode/Layer A/electrode is connected, if desired, to a current
collecting body, and after placing it in a structure constituting a
capacitor or when the current collecting body also serves as a
structure constituting a capacitor as such, the structure is
subjected to known processing, for example, sealing of an open edge
part with an insulating sealant such as an epoxy resin or
polyolefin resin, to thereby obtain a capacitor.
[0232] In the production method of a capacitor of the present
invention, at any step before production of a laminate consisting
of electrode/Layer A/electrode, the above-described current
collecting body may be previously connected to the electrode.
[0233] According to the production method of a capacitor using the
ion conductive laminate of the present invention, a high-quality,
for example, whole solid electrical double layer capacitor using a
whole solid type SPE or PGE having a homogenous thickness can be
produced. In particular, by using the ion conductive laminate of
the present invention in the production of a capacitor, a thin
whole solid type electrical double layer capacitor can be produced
which has a very thin SPE or PGE layer having a homogenous
thickness in good contact with the electrode. Accordingly, the
resulting capacitor has excellent electrical properties, namely, a
rapid charge/discharge property, high coulombic efficiency and
cyclability.
[0234] The shape of the electrical double layer capacitor may be,
in addition to a sheet form as shown in FIG. 10, a coin form or a
cylindrical form which is produced by rolling a sheet laminate of
polarizable electrodes and a SPE or PGE into a cylinder, placing it
in a cylindrical tube-type structure constituting the capacitor,
and sealing the structure.
[0235] In producing a roll-type capacitor, similarly to the
production method of a roll-type battery described above, a method
where a film laminate consisting, for example, of a polarizable
electrode/Layer A/polarizable electrode/Layer A is prepared, rolled
and inserted into a structure constituting a capacitor may also be
used. The above-described curable substance or a mixture thereof is
further injected therein and polymerized.
[0236] The ion conductive laminate of the present invention can be
produced, for example, as a laminate having an extremely large area
or an extremely large length, for example, 120 mm in width and
several hundreds of meters or more in length, by an extrusion
molding and wound into a rolled laminate. The laminate of the
present invention is characterized, as one of its important
characteristic features, in that it can be provided as a laminate
having a large-area and a homogenized ion conductive material film.
This cannot be achieved by conventional ion conductive materials.
The laminate may be cut into a desired size at any stage depending
upon the intended application. Accordingly, electrochemical
elements and apparatuses having a homogenized ion conductive
material layer having an optional thickness and an extremely large
area can be produced. Also, the laminate of the present invention
can be cut into an extremely fine size and therefore,
electrochemical elements and apparatuses having an extremely small,
thin and homogenized ion conductive material film can be
produced.
EXAMPLES
[0237] The present invention is described in greater detail by
reference to the following Examples. However, these Examples are
set forth for description only, and the present invention should
not be construed as being limited thereto.
Example 1
[0238] 1
[0239] wherein [X.sup.1] represents
(CH.sub.2CH.sub.2O).sub.p[CH(CH.sub.3)- CH.sub.2O].sub.qH and
[X.sup.2] represents 2
[0240] Synthesis of Compound 3:
[0241] In 100 ml of purified THF, 57.7 g of Compound 1 (KOH value:
34.0 mg/g, p/q=4) and 3.89 g of Compound 2 were dissolved under a
nitrogen atmosphere, and thereto 0.44 g of dibutyltin dilaurate was
added. Thereafter, the mixture was reacted at 25.degree. C. for
about 15 hours to obtain a colorless viscous liquid. From the
results of .sup.1H-NMR, IR and elemental analysis thereof, it was
verified that Compound 1 and Compound 2 were reacted at a molar
ratio of 1:3, the isocyanate group of Compound 2 disappeared, a
urethane bond was produced, and Compound 3 was produced.
Example 2
[0242] Under an argon atmosphere, 1.50 g of Compound 3, 1.5 g of
diethyl carbonate (DEC), 1.5 g of ethylene carbonate (EC), 0.30 g
of LiBF.sub.4 and 0.02 g of Irgacure 500 (produced by Ciba Geigy
AG) were well mixed to obtain a photopolymerizable monomer
solution.
[0243] The resulting polymerizable monomer solution was coated on
an alumina layer of a PET film (50 .mu.m-thick) having
vapor-deposited thereon a 500 .ANG.-thick alumina layer, under a
nitrogen atmosphere by means of a coater to a thickness of 30 .mu.m
and cured by irradiating under a mercury lamp for 10 minutes to
obtain a transparent solid polymer electrolyte (SPE) layer.
Furthermore, on the SPE layer, a polypropylene film (30
.mu.m-thick) was superposed under a nitrogen atmosphere by means of
nip rolls to obtain a film laminate consisting of
PET/alumina/SPE/polypropylene.
[0244] The ion conductivity at 25.degree. C. of the SPE layer of
the laminate was measured by an impedance method and determined to
be 2.times.10.sup.-3 S/cm.
[0245] The water content of the SPE layer was 100 ppm (according to
Karl Fischer's method). The laminate was stored in a thermostatic
chamber at a temperature of 23.degree. C. and a humidity of 60% RH
for one hour. Then, the water content of the SPE layer was 120 ppm
and had hardly increased from its value prior to storage. The ion
conductivity did not change and was 2.times.10.sup.-3 S/cm.
[0246] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 1,500 ppm and the ion conductivity
was reduced to 0.7.times.10.sup.-3 S/cm.
[0247] The polypropylene and/or PET film as an upper or lower layer
could be peeled off from the laminate and the SPE layer could be
easily laminated on another substrate such as an electrode.
Example 3
[0248] A film laminate consisting of PET/alumina/SPE/polypropylene
was obtained in the same manner as in Example 2, except for using
0.40 g of NaCF.sub.3SO.sub.3 in place of the LiBF.sub.4 used in
Example 2. The ion conductivity at 25.degree. C. of the SPE layer
of the laminate was measured by an impedance method and determined
to be 5.times.10.sup.-3 S/cm. The water content of the SPE layer
was 90 ppm (according to Karl Fischer's method). The laminate was
stored in a thermostatic chamber at a temperature of 23.degree. C.
and a humidity of 60% RH for one hour. Then, the water content of
the SPE layer was 150 ppm and had hardly increased from its value
prior to storage. The ion conductivity did not change and was
5.times.10.sup.-3 S/cm.
[0249] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 3,000 ppm and the ion conductivity
was reduced to 2.times.10.sup.-3 S/cm.
[0250] The polypropylene and/or PET film as an upper or lower layer
could be peeled off from the laminate and the SPE layer could be
easily laminated on other substrate such as an electrode.
Example 4
[0251] A film laminate consisting of aluminum/SPE/polypropylene was
obtained in the same manner as in Example 2, except for using a 25
.mu.m-thick aluminum foil in place of the alumina-evaporated PET
film used in Example 2. The ion conductivity at 25.degree. C. of
the SPE layer of the laminate was measured by an impedance method
and determined to be 2.times.10.sup.-3 S/cm. The water content of
the SPE layer was 100 ppm (according to Karl Fischer's method). The
laminate was stored in a thermostatic chamber at a temperature of
23.degree. C. and a humidity of 60% RH for one hour. Then, the
water content of the SPE layer was 115 ppm and had hardly increased
from its value prior to storage. The ion conductivity did not
change and was 2.times.10.sup.-3 S/cm.
[0252] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 3,200 ppm and the ion conductivity
was reduced to 0.8.times.10.sup.-3 S/cm.
[0253] The polypropylene film and/or aluminum foil as an upper or
lower layer could be peeled off from the laminate and the SPE layer
could be easily laminated on another substrate such as an
electrode.
Example 5
[0254] 3
[0255] wherein [X.sup.3] represents a 2:1 mixture group of
(CH.sub.2CH.sub.2O).sub.p[CH(CH.sub.3)CH.sub.2O].sub.qH and
(CH.sub.2CH.sub.2O).sub.p[CH(CH.sub.3)CH.sub.2O].sub.qCH.sub.3, and
[X.sup.4] represents a 2:1 mixture group of 4
[0256] and
(CH.sub.2CH.sub.2O).sub.p[CH(CH.sub.3)CH.sub.2O].sub.qCH.sub.3.
[0257] Synthesis of Compound 6:
[0258] In 100 ml of purified THF, 38.5 g of Compound 4 (KOH value:
22.7 mg/g, p/q=5) and 2.42 g of Compound 5 were dissolved under a
nitrogen atmosphere, and thereto 0.29 g of dibutyltin dilaurate was
added. Thereafter, the mixture was reacted at 25.degree. C. for
about 15 hours to obtain a colorless viscous liquid. From the
results of .sup.1H-NMR, IR and elemental analysis thereof, it was
verified that Compound 4 and Compound 5 were reacted at a molar
ratio of 1:2, the isocyanate group of Compound 5 disappeared, a
urethane bond was produced, and Compound 6 was produced.
Example 6
[0259] Under an argon atmosphere, 1.50 g of Compound 6, 2.0 g of
.gamma.-butyrolactone (GBL), 2.0 g of ethylene carbonate (EC), 0.35
g of LiClO.sub.4 and 0.02 g of Irgacure 500 (produced by Ciba Geigy
AG) were well mixed to obtain a photopolymerizable monomer
solution.
[0260] The resulting polymerizable monomer solution was coated on
the aluminum layer of a PET film (50 .mu.m-thick) having
vapor-deposited thereon a 100 .ANG.-thick aluminum layer, under a
nitrogen atmosphere by means of a coater to a thickness of 30 .mu.m
and irradiated under a mercury lamp for 1 minute to form a SPE
layer. Furthermore, on the SPE layer, a polypropylene film (30
.mu.m-thick) was laminated and irradiated under a mercury lamp for
10 minutes to obtain a film laminate consisting of
PET/aluminum/SPE/polypropylene. The ion conductivity at 25.degree.
C. of the SPE layer of the laminate was measured by an impedance
method and determined to be 3.5.times.10.sup.-3 S/cm. The water
content of the SPE layer was 150 ppm (according to Karl Fischer's
method). The laminate was stored in a thermostatic chamber at a
temperature of 23.degree. C. and a humidity of 60% RH for one hour.
Then, the water content of the SPE layer was then 180 ppm and had
hardly increased from its value prior to storage. The ion
conductivity did not change and was 3.5.times.10.sup.-3 S/cm.
[0261] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 2,000 ppm and the ion conductivity
was slightly reduced to 2.5.times.10.sup.-3 S/cm.
[0262] The polypropylene and/or PET film as an upper or lower layer
could be peeled off from the laminate and the SPE layer could be
easily laminated on another substrate such as an electrode.
Example 7
[0263] A film laminate consisting of PET/aluminum/SPE/polypropylene
was obtained in the same manner as in Example 6 except for using
the same amount of tetraglyme (TG) in place of the GBL used in
Example 6. The ion conductivity at 25.degree. C. of the SPE layer
of the laminate was measured by an impedance method and determined
to be 1.5.times.10.sup.-3 S/cm. The water content of the SPE layer
was 90 ppm (according to Karl Fischer's method). The laminate was
stored in a thermostatic chamber at a temperature of 23.degree. C.
and a humidity of 60% RH for one hour. Then, the water content of
the SPE layer was 150 ppm and had hardly increased from its value
prior to storage. The ion conductivity did not change and was
1.5.times.10.sup.-3 S/cm.
[0264] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 3,000 ppm and the ion conductivity
did not change and was 1.5.times.10.sup.-3 S/cm.
[0265] The polypropylene and/or PET film as an upper or lower layer
could be peeled off from the laminate and the SPE layer could be
easily laminated on another substrate such as an electrode.
Example 8
[0266] 5
[0267] Synthesis of Compound 8:
[0268] In 100 ml of purified THF, 55 g of Compound 7 (average
molecular weight Mn=550) and 15 g of Compound 5 were dissolved
under a nitrogen atmosphere, and thereto 0.66 g of dibutyltin
dilaurate was added. Thereafter, the mixture was reacted at
25.degree. C. for about 15 hours to obtain a colorless viscous
liquid. From the results of .sup.1H-NMR, IR and elemental analysis
thereof, it was verified that Compound 7 and Compound 5 were
reacted at a molar ratio of 1:1, the isocyanate group of Compound 5
disappeared, a urethane bond was produced, and Compound 8 was
produced.
Example 9
[0269] Under an argon atmosphere, to a mixture of 1.5 g of Compound
8 and 0.10 g of LiClO.sub.4, 0.01 g of Dalocure 1173 (produced by
Ciba Geigy AG) was added and well mixed to obtain a polymerizable
monomer solution.
[0270] The resulting polymerizable monomer solution was coated on a
high-density polyethylene film (30 .mu.m-thick) subjected to corona
discharge treatment, under a nitrogen atmosphere by means of a
coater to a thickness of 30 .mu.m and irradiated under a mercury
lamp for 1 minute to form a SPE layer. Thereafter, on the SPE
layer, a polypropylene film (30 .mu.m-thick) was laminated and
irradiated under a mercury lamp for 10 minutes to obtain a film
laminate consisting of polyethylene/SPE/polyprop- ylene. The ion
conductivity at 25.degree. C. of the SPE layer of the laminate was
measured by an impedance method and determined to be
1.times.10.sup.-4 S/cm. The water content of the SPE layer was 180
ppm (according to Karl Fischer's method). The laminate was stored
in a thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. Then, the water content of the SPE
layer was 180 ppm which was the same as its value prior to storage.
Also, the ion conductivity did not change and was 1.times.10.sup.-4
S/cm.
[0271] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 800 ppm but the ion conductivity did
not change and was 1.times.10.sup.-4 S/cm.
[0272] The polyethylene film and/or polypropylene film as an upper
or lower layer could be peeled off from the laminate and the SPE
layer could be easily laminated on another substrate such as an
electrode.
Example 10
[0273] A film laminate consisting of PET/SPE/polypropylene was
obtained in the same manner as in Example 9 except for using a 50
.mu.m-thick PET film in place of the high-density polyethylene film
subjected to corona discharge treatment as used in Example 9. The
ion conductivity at 25.degree. C. of the SPE layer of the laminate
was measured by an impedance method and determined to be
1.times.10.sup.-4 S/cm. The water content of the SPE layer was 180
ppm (according to Karl Fischer's method). The laminate was stored
in a thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. Then, the water content of the SPE
layer was 230 ppm and had hardly changed from its value prior to
storage. Also, the ion conductivity did not change and was
1.times.10.sup.-4 S/cm.
[0274] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 1,000 ppm but the ion conductivity
did not change and was 1.times.10.sup.-4 S/cm.
[0275] The polypropylene and/or PET film as an upper or lower layer
could be peeled off from the laminate and the SPE layer could be
easily laminated on another substrate such as an electrode.
Example 11
[0276] A film laminate consisting of PET/alumina/SPE/polypropylene
was obtained in the same manner as in Example 2, except for using
0.50 of tetraethylammonium tetrafluoroborate (TEAB) in place of the
LiBF.sub.4 used in Example 2. The ion conductivity at 25.degree. C.
of the SPE layer of the laminate was measured by an impedance
method and determined to be 3.times.10.sup.-3 S/cm. The water
content of the SPE layer was 300 ppm (according to Karl Fischer's
method). The laminate was stored in a thermostatic chamber at a
temperature of 23.degree. C. and a humidity of 60% RH for one hour.
Then, the water content of the SPE layer was 350 ppm and had hardly
increased from its value prior to storage. The ion conductivity did
not change and was 3.times.10.sup.-3 S/cm.
[0277] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 3,500 ppm and the ion conductivity
was reduced to 1.times.10.sup.-3 S/cm. The polypropylene and/or PET
film as an upper or lower layer could be peeled off from the
laminate and the SPE layer could be easily laminated on another
substrate such as an electrode.
Example 12
[0278] A film laminate consisting of PET/alumina/SPE/polypropylene
was obtained in the same manner as in Example 2, except for using
0.35 of LiPF.sub.6 in place of the LiBF.sub.4 used in Example 2.
The ion conductivity at 25.degree. C. of the SPE layer of the
laminate was measured by an impedance method and determined to be
2.5.times.10.sup.-3 S/cm. The water content of the SPE layer was 80
ppm (according to Karl Fischer's method). The laminate was stored
in a thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. Then, the water content of the SPE
layer was 80 ppm and did not increase from its value prior to
storage. The ion conductivity did not change and was
2.5.times.10.sup.-3 S/cm.
[0279] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 3,500 ppm and the ion conductivity
was reduced to 0.5.times.10.sup.-3 S/cm.
[0280] The polypropylene and/or PET film as an upper or lower layer
could be peeled off from the laminate and the SPE layer could be
easily laminated on another substrate such as an electrode.
Example 13
[0281] Under an argon atmosphere, to a mixture of 1.50 g of
Compound 3 and 0.2 g of N,N-dimethylacrylamide, 1.5 g of
.gamma.-butyrolactone (GBL), 1.5 g of ethylene carbonate (EC), 0.30
g of LiBF.sub.4 and 0.02 g of Irgacure 500 (produced by Ciba Geigy
AG) were well mixed to obtain a photopolymerizable monomer
solution.
[0282] The resulting photopolymerizable monomer solution was
impregnated into a 30 .mu.m-thick polypropylene-made nonwoven
fabric (MU3005, produced by Japan Vilene Co.), provided on a
polypropylene film (30 .mu.m-thick) under a nitrogen atmosphere and
cured by irradiating with a mercury lamp for 10 minutes to obtain a
non-woven fabric compounded SPE layer. Furthermore, on the layer, a
polypropylene film (30 .mu.m-thick) was laminated under a nitrogen
atmosphere by means of nip rolls to obtain a film laminate
consisting of polypropylene/SPE/polypropylene. The ion conductivity
at 25.degree. C. of the SPE layer was measured by an impedance
method and determined to be 1.0.times.10.sup.-3 S/cm. The water
content of the SPE layer was 100 ppm (according to Karl Fischer's
method).
[0283] The laminate was stored in a thermostatic chamber at a
temperature of 23.degree. C. and a humidity of 60% RH for one hour.
Then, the water content of the solid polymer electrolyte layer was
110 ppm and had hardly increased from its value prior to storage.
The ion conductivity did not change and was 1.times.10.sup.-3
S/cm.
[0284] The polypropylene film on one side was peeled off from the
laminate and in the same manner as above, the laminate was stored
in a thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 1,500 ppm, and the ion conductivity
was slightly reduced to 0.8.times.10.sup.-3 S/cm.
[0285] The polypropylene film on one side or on both sides as an
upper or lower layer could be peeled off from the laminate and the
SPE layer could be easily laminated on another substrate such as an
electrode.
Example 14
[0286] Under an argon atmosphere, to a mixture of 1.50 g of
Compound 3 and 0.2 g of polyethylene oxide having an average
molecular weight of 10,000 (produced by Aldrich KK), 1.5 g of
.gamma.-butyrolactone (GBL), 1.5 g of ethylene carbonate (EC), 0.30
g of LiBF.sub.4 and 0.02 g of Irgacure 500 (produced by Ciba Geigy
AG) were well mixed to obtain a photopolymerizable monomer
solution.
[0287] The resulting photopolymerizable monomer solution was
impregnated into a 150 .mu.m-thick general purpose grade
polyethylene net, provided on a PET film (50 .mu.m-thick) under a
nitrogen atmosphere and cured by irradiating with a mercury lamp
for 10 minutes to obtain a non-woven fabric compounded SPE layer.
Furthermore, on the SPE layer, a polypropylene film (30
.mu.m-thick) was laminated by means of nip rolls to obtain a film
laminate consisting of PET/SPE/polypropylene.
[0288] The ion conductivity at 25.degree. C. of the SPE layer of
the laminate was measured by an impedance method and determined to
be 1.5.times.10.sup.-3 S/cm. The water content of the SPE layer was
100 ppm (according to Karl Fischer's method). The laminate was
stored in a thermostatic chamber at a temperature of 23.degree. C.
and a humidity of 60% RH for one hour. Then, the water content of
the SPE layer was 120 ppm and had hardly increased from its value
prior to storage. The ion conductivity did not change and was
1.5.times.10.sup.-3 S/cm.
[0289] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 2,000 ppm and the ion conductivity
was slightly reduced to 1.0.times.10.sup.-3 S/cm.
[0290] The polypropylene and/or PET film as an upper or lower layer
could be peeled off from the laminate and the SPE layer could be
easily laminated on another substrate such as an electrode.
Example 15
[0291] Under an argon atmosphere, 1.50 g of Compound 3, 1.5 g of
.gamma.-butyrolactone (GBL), 1.5 g of ethylene carbonate (EC), 0.30
g of LiClO.sub.4 and 0.001 g of azobisisobutyronitrile (AIBN) were
well mixed to obtain a thermopolymerizable monomer solution.
[0292] The thermopolymerizable monomer solution was coated on an
alumina layer of a PET film (50 .mu.m-thick) having vapor-deposited
thereon a 500 .ANG.-thick alumina layer, under a nitrogen
atmosphere by means of a coater to a thickness of about 30 .mu.m.
This structure was heated at 60.degree. C. for 5 minutes to
partially polymerize and thereby increase the viscosity of the
thermopolymerizable monomer solution layer. Thereon, a
polypropylene film (30 .mu.m-thick) was superposed and heated at
60.degree. C. for one hour to completely cure the polymerizable
monomer solution, to thereby obtain a film laminate consisting of
PET/alumina/SPE/polypropylene.
[0293] The ion conductivity at 25.degree. C. of the SPE layer was
measured by an impedance method and determined to be
1.5.times.10.sup.-3 S/cm. The water content of the SPE layer was
100 ppm (according to Karl Fischer's method). The laminate was
stored in a thermostatic chamber at a temperature of 23.degree. C.
and a humidity of 60% RH for one hour. Then, the water content of
the SPE layer was 120 ppm and had hardly increased from its value
prior to storage. The ion conductivity did not change and was
1.5.times.10.sup.-3 S/cm.
[0294] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 2,100 ppm and the ion conductivity
was slightly reduced to 1.0.times.10.sup.-3 S/cm.
[0295] The polypropylene and/or PET film as an upper or lower layer
could be peeled off from the laminate and the SPE layer could be
easily laminated on another substrate such as an electrode.
Example 16
[0296] Under an argon atmosphere, 2.0 g of polyethylene oxide
having an average molecular weight of 10,000 (produced by Aldrich
KK) was dissolved in about 20 g of 1,2-dimethoxyethane (DME) and
then 0.20 g of LiClO.sub.4 was dissolved therein to obtain a SPE
solution.
[0297] The resulting SPE solution was coated on an alumina layer of
a PET film (50 .mu.m-thick) having vapor-deposited thereon a 500
.ANG.-thick alumina layer, by means of a coater to a thickness of
about 100 .mu.m, and dried for 2 hours under a nitrogen atmosphere.
Furthermore, a polypropylene film (30 .mu.m-thick) was laminated on
the SPE layer under a nitrogen atmosphere by means of nip rolls to
obtain a film laminate consisting of PET/alumina/SPE/polypropylene.
The laminate was further vacuum dried at room temperature for one
hour to remove the remaining DME solution.
[0298] The ion conductivity at 25.degree. C. of the SPE layer of
the laminate was measured by an impedance method and determined to
be 1.times.10.sup.-6 S/cm. The water content of the SPE layer was
500 ppm (according to Karl Fischer's method). The laminate was
stored in a thermostatic chamber at a temperature of 23.degree. C.
and a humidity of 60% RH for one hour. Then, the water content of
the SPE layer was 500 ppm and had not changed from its value prior
to storage. The ion conductivity did not change and was
1.times.10.sup.-6 S/cm.
[0299] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 1,000 ppm but the ion conductivity
did not change.
[0300] The polypropylene and/or PET film as an upper or lower layer
could be peeled off from the laminate and the SPE layer could be
easily laminated on another substrate such as an electrode.
Example 17
[0301] Under an argon atmosphere, to a mixture of 1.5 g of
methacryl-modified polyethylene glycol (Blenmer PME 400, produced
by Nippon Oils & Fats Co., Ltd., average molecular weight: 400)
and0.10 g of LiClO.sub.4, 0.01 g of Dalocure 1173 (produced by Ciba
Geigy AG) were added and well mixed under an argon atmosphere to
obtain a photopolymerizable monomer solution.
[0302] The resulting photopolymerizable monomer solution was coated
on a polyethylene film (30 .mu.m-thick) subjected to corona
discharge treatment, under a nitrogen atmosphere by means of a
coater to a thickness of 30 .mu.m and irradiated with a mercury
lamp for 1 minute to form a SPE layer. Thereafter, on the SPE
layer, a polypropylene film (30 .mu.m-thick) was superposed and
then irradiated with a mercury lamp for 10 minutes to obtain a film
laminate consisting of polyethylene/SPE/polypropylene.
[0303] The ion conductivity at 25.degree. C. of the SPE layer of
the laminate was measured by an impedance method and determined to
be 1.times.10.sup.-5 S/cm. The water content of the SPE layer was
150 ppm (according to Karl Fischer's method). The laminate was
stored in a thermostatic chamber at a temperature of 23.degree. C.
and a humidity of 60% RH for one hour. Then, the water content of
the SPE layer was 160 ppm which was almost the same as its value
prior to storage. The ion conductivity did not change and was
1.times.10.sup.-5 S/cm.
[0304] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 2,000 ppm but the ion conductivity
did not change and was 1.times.10.sup.-5 S/cm.
[0305] The polypropylene and/or PET film as an upper or lower layer
could be peeled off from the laminate and the SPE layer could be
easily laminated on another substrate such as an electrode.
Example 18
[0306] Under an argon atmosphere, to a mixture of 0.75 g of
urethane acrylate (UA-101H, produced by Kyoei Sha Yushi Kagaku KK,
glycerin dimethacrylate hexamethylenediisocyanate urethane
prepolymer) and 0.75 g of polyethylene oxide having an average
molecular weight of 5,000 (produced by Aldrich KK), 1.5 g of 65
-butyrolactone (GBL), 1.5 g of ethylene carbonate, 0.30 g of
LiBF.sub.4 and 0.02 g of Irgacure 500 (produced by Ciba Geigy AG)
were well mixed under an argon atmosphere to obtain a
photopolymerizable monomer solution.
[0307] The resulting photopolymerizable monomer solution was coated
on a silicon dioxide layer of a PET film (50 .mu.m-thick) having
vapor-deposited thereon a 100 .ANG.-thick silicon dioxide layer,
under a nitrogen atmosphere by means of a coater to a thickness of
30 .mu.m and irradiated with a mercury lamp for 5 minutes to form a
SPE layer. Thereafter, on the SPE layer, a polypropylene film (30
.mu.m-thick) was laminated and then irradiated with a mercury lamp
for 20 minutes to obtain a film Laminate consisting of PET/silicon
dioxide/SPE/polypropylen- e.
[0308] The ion conductivity at 25.degree. C. of the SPE layer was
measured by an impedance method and determined to be
3.times.10.sup.-4 S/cm. The water content of the SPE layer was 300
ppm (according to Karl Fischer's method). The laminate was stored
in a thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. Then, the water content of the SPE
layer was 330 ppm and had hardly increased from its value prior to
storage. The ion conductivity did not change and was
3.times.10.sup.-4 S/cm.
[0309] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 1,500 ppm and the ion conductivity
was reduced to 1.0.times.10.sup.-4 S/cm.
[0310] The polypropylene and/or PET film as an upper or lower layer
could be peeled off from the laminate and the SPE layer could be
easily laminated on another substrate such as an electrode.
Example 19
[0311] Under an argon atmosphere, to 1.5 g of polyethylene glycol
dimethacrylate (Blenmer PDE-600, produced by Nippon Oils &
Facts Co., Ltd.; average molecular weight: 600), 1.0 g of
.gamma.-butyrolactone (GBL), 1.0 g of ethylene carbonate (EC), 0.30
g of LiBF.sub.4 and 0.02 g of Irgacure 651 (produced by Ciba Geigy
AG) were well mixed to obtain a photopolymerizable monomer
solution.
[0312] The resulting photopolymerizable monomer solution was coated
on a silicon dioxide layer of a PET film (50 .mu.m-thick) having
vapor-deposited thereon a 100 .ANG.-thick silicon dioxide layer,
under a nitrogen atmosphere by means of a coater to a thickness of
30 .mu.m and irradiated with a mercury lamp for 5 minutes to form a
SPE layer. Thereafter, on the SPE layer, a polypropylene film (30
.mu.m-thick) was laminated and then irradiated with a halogen lamp
for 30 minutes to obtain a film laminate consisting of PET/silicon
dioxide/SPE/polypropylen- e.
[0313] The ion conductivity at 25.degree. C. of the SPE layer of
the laminate was measured by an impedance method and determined to
be 1.times.10.sup.-4 S/cm. The water content of the SPE layer was
350 ppm (according to Karl Fischer's method). The laminate was
stored in a thermostatic chamber at a temperature of 23.degree. C.
and a humidity of 60% RH for one hour. Then, the water content of
the SPE layer was 360 ppm and had hardly increased from its value
prior to storage. The ion conductivity did not change and was
1.times.10.sup.-4 S/cm.
[0314] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 2,500 ppm and the ion conductivity
was reduced to 0.7.times.10.sup.-4 S/cm.
[0315] The polypropylene and/or PET film as an upper or lower layer
could be peeled off from the laminate and the SPE layer could be
easily laminated on another substrate such as an electrode.
Example 20
[0316] Under an argon atmosphere, 3.0 g of an acrylonitrile
(ACN)/methacrylate (MA) copolymer (produced by Toyobo KK, ACN/MA=
20/1 by mol) was swollen with 8.0 g of ethylene carbonate (EC) and
10.0 g of propylene carbonate (PC) and then 2.3 g of LiClO.sub.4
was dissolved therein to obtain a polymer gel electrolyte
(PGE).
[0317] The resulting PGE was spread on a PET film (50 .mu.m-thick)
by means of a spatula and on the PGE layer, a polypropylene film
(30 .mu.m-thick) was laminated under a nitrogen atmosphere and
subjected to roll press molding to a thickness of the PGE layer of
100 .mu.m, to thereby obtain a film laminate consisting of
PET/PGE/polypropylene.
[0318] The ion conductivity at 25.degree. C. of the PGE layer of
the laminate was measured by an impedance method and determined to
be 1.times.10.sup.-3 S/cm. The water content of the PGE layer was
100 ppm (according to Karl Fischer's method). The laminate was
stored in a thermostatic chamber at a temperature of 23.degree. C.
and a humidity of 60% RH for one hour. Then, the water content of
the PGE layer was 150 ppm and had hardly increased from its value
prior to storage. The ion conductivity did not change and was
1.times.10.sup.-3 S/cm.
[0319] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the PGE layer was increased to 1,000 ppm. The ion conductivity did
not change.
[0320] The polypropylene and/or PET film as an upper or lower layer
could be peeled off from the laminate and the PGE layer could be
easily laminated on another substrate such as an electrode.
Example 21
[0321] Under an argon atmosphere, 3.0 g of an acrylonitrile
(ACN)/methacrylate (MA) copolymer (produced by Toyobo KK,
ACN/MA=20/1 by mol) was swollen with 8.0 g of ethylene carbonate
(EC) and 10.0 g of propylene carbonate (PC) and then 2.3 g of
LiClO.sub.4 was dissolved therein to obtain a PGE. Subsequently, 5
g of spectral grade acetonitrile (AN, produced by Wako Junyaku) was
added thereto to obtain a PGE solution.
[0322] The resulting PGE solution was coated on an alumina layer of
a PET film (50 .mu.m-thick) having vapor-deposited thereon a 500
.ANG.-thick alumina, under a nitrogen atmosphere by means of a
coater to a thickness of 200 .mu.m, and dried for 2 hours under a
nitrogen atmosphere. Furthermore, a polypropylene film (30
.mu.m-thick) was laminated on the PGE layer under a nitrogen
atmosphere by means of nip rolls to obtain a laminate, and the
laminate was further vacuum dried at room temperature at 60.degree.
C. for one hour to remove the remaining AN to thereby obtain a film
laminate consisting of PET/alumina/PGE/polypropylene including a
PGE layer having a thickness of about 100 .mu.m.
[0323] The ion conductivity at 25.degree. C. of the PGE layer of
the laminate was measured by an impedance method and determined to
be 1.2.times.10.sup.-3 S/cm. The water content of the PGE layer was
110 ppm (according to Karl Fischer's method). The laminate was
stored in a thermostatic chamber at a temperature of 23.degree. C.
and a humidity of 60% RH for one hour. Then, the water content of
the PGE layer was 150 ppm and had hardly increased from its value
prior to storage. The ion conductivity did not change and was
1.2.times.10.sup.-3 S/cm.
[0324] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the PGE layer was increased to 1,400 ppm. The ion conductivity was
1.0.times.10.sup.-3 S/cm and slightly reduced.
[0325] The polypropylene and/or PET film as an upper or lower layer
could be peeled off from the laminate and the PGE layer could be
easily laminated on another substrate such as an electrode.
Example 22
[0326] Under an argon atmosphere, 3.0 g of polyvinylidene fluoride
(PVdF, Battery Binder Grade, produced by Kuraray KK) was swollen
with 10.0 g of ethylene carbonate (EC) and 10.0 g of
.gamma.-butyrolactone (GBL) and then 3.0 g of LiBF.sub.4 was
dissolved therein to obtain a PGE.
[0327] The resulting PGE was spread on a polypropylene film (30
.mu.m-thick) by means of a spatula and further on the PGE layer, a
polypropylene film (30 .mu.m-thick) was superposed under a nitrogen
atmosphere and subjected to roll press molding to a PGE layer
thickness of 100 .mu.m to thereby obtain a film laminate consisting
of polypropylene/PGE/polypropylene.
[0328] The ion conductivity at 25.degree. C. of the PGE layer of
the laminate was measured by an impedance method and determined to
be 8.times.10.sup.-4 S/cm. The water content of the PGE layer was
120 ppm (according to Karl Fischer's method). The laminate was
stored in a thermostatic chamber at a temperature of 23.degree. C.
and a humidity of 60% RH for one hour. Then, the water content of
the PGE layer was 140 ppm and had hardly increased from its value
prior to storage. The ion conductivity was almost unchanged and was
6.times.10.sup.-4 S/cm.
[0329] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the PGE layer was increased to 3,000 ppm. The ion conductivity was
reduced to 3.times.10.sup.-4 S/cm.
[0330] The polypropylene film on one side or on both sides as an
upper or lower layer could be peeled off from the laminate and the
PGE layer could be easily laminated on another substrate such as an
electrode.
Example 23
[0331] Production of lithium cobaltate/aluminum foil laminate
electrode:
[0332] Li.sub.2CO.sub.3 (11 g) and 24 g of Co.sub.3O.sub.4 were
well mixed, heated at 800.degree. C. for 24 hours under an oxygen
atmosphere and crushed to obtain a LiCoO.sub.2 powder. The
LiCoO.sub.2 powder, acetylene black and polyvinylidene fluoride
were mixed at a weight ratio of 8:1:1, and thereto excess
N-methylpyrrolidone was added to obtain a gelled composition. The
composition thus obtained was coated on an aluminum foil having a
thickness of about 25 .mu.m in a size of 10 cm.times.10 cm and then
roll molded to a thickness of about 50 .mu.m. The molding was
vacuum dried under heating at about 100.degree. C. for 24 hours to
obtain a lithium cobaltate/aluminum foil laminate electrode.
Example 24
[0333] Under an argon atmosphere, 1.50 g of Compound 6, 2.0 g of
.gamma.-butyrolactone (GBL), 2.0 g of ethylene carbonate (EC), 0.35
g of LiClO.sub.4 and 0.02 g of Irgacure 500 (produced by Ciba Geigy
AG) were well mixed to obtain a photopolymerizable monomer
solution.
[0334] The resulting photopolymerizable monomer solution was coated
on a lithium cobaltate layer of a cut portion of the lithium
cobaltate/aluminum foil laminate electrode produced in Example 23,
under a nitrogen atmosphere by means of a coater to a thickness of
30 .mu.m and irradiated with a mercury lamp for 1 minute to form a
SPE layer. Thereafter, on the SPE layer, a polypropylene film (30
.mu.m-thick) was laminated and then irradiated with a mercury lamp
for 10 minutes to obtain a film laminate consisting of
aluminum/lithium cobaltate/SPE/polypropylene.
[0335] The water content of the SPE layer of the laminate was 80
ppm (according to Karl Fischer's method). The laminate was stored
in a thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. Then, the water content of the SPE
layer was 100 ppm and had hardly increased from its value prior to
storage.
[0336] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was allowed to stand in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer increased to 5,000 ppm.
Example 25
[0337] A film laminate consisting of aluminum/lithium
cobaltate/SPE/alumina/PET was obtained in the same manner as in
Example 24 except for using a PET film (50 .mu.m-thick) having
vapor-deposited thereon an alumina layer having a thickness of 500
.ANG. in place of the polypropylene film used in Example 24.
[0338] The water content of the SPE layer of the laminate was 85
ppm (according to Karl Fischer's method). The laminate was stored
in a thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. Then, the water content of the SPE
layer was 100 ppm and had hardly increased from its value prior to
storage.
[0339] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer increased to 4,300 ppm.
Example 26
[0340] Production of graphite/copper foil laminate electrode:
[0341] To a mixture of MCMB graphite (average particle size: 5
.mu.m) produced by Osaka Gas K.K., a vapor phase process graphite
fiber (average fiber size: 0.3 .mu.m, average fiber length: 2.0
.mu.m, heat treated product at 2,700.degree. C.) produced by Showa
Denko K.K., and polyvinylidene fluoride (PVdF) at a weight ratio of
8.6:0.4:1.0, and excess N-methylpyrrolidone was added to obtain a
gelled composition. The composition thus obtained was coat-molded
on copper foil of about 15 .mu.m-thick into a size of 10
cm.times.10 cm and a thickness of about 50 .mu.m. The molding was
vacuum dried under heating at about 100.degree. C. for 24 hours to
obtain a graphite/copper foil laminate electrode.
Example 27
[0342] The photopolymerizable monomer solution prepared in Example
24 was coated on a graphite layer of a cut portion of the
graphite/copper foil laminate electrode prepared in Example 26,
under a nitrogen atmosphere by means of a coater to have a
thickness of 30 .mu.m and then irradiated with a mercury lamp for 1
minute to form a SPE layer. On the SPE layer, a polypropylene film
(30 .mu.m-thick) was laminated and further irradiated with a
mercury lamp for 10 minutes to obtain a film laminate consisting of
aluminum/lithium cobaltate/SPE/polypropylene.
[0343] The water content of the SPE layer of the laminate was 80
ppm (according to Karl Fischer's method). The laminate was stored
in a thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. Then, the water content of the SPE
layer was 100 ppm and had hardly increased from its value prior to
storage. The polypropylene film was peeled off from the laminate
and in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer increased to 4,800 ppm.
Example 28
[0344] Production of Li secondary battery:
[0345] Under an argon atmosphere, 1.5 g of Compound 6, 2.0 g of
.gamma.-butyrolactone (GBL), 2.0 g of ethylene carbonate (EC), 0.35
g of LiClO.sub.4 and 0.001 g of benzoyl peroxide were well mixed to
obtain a thermopolymerizable monomer solution.
[0346] In a glove box under an argon atmosphere, a 25 .mu.m-thick
lithium foil was cut into a size of 12 mm.times.12 mm and bonded
under pressure to a copper foil (15 .mu.m-thick) in a size of 12
mm.times.12 mm. The periphery of about 1 mm from four edges thereof
was covered by a 5 .mu.m-thick polyimide film as a spacer and the
photopolymerizable monomer solution prepared in Example 24 was
thinly (about 1 .mu.m) coated on the Li foil. Then, the film
laminate produced in Example 2 was cut into a size of 12
mm.times.12 mm, the polypropylene film layer was peeled off
therefrom, the SPE layer was laminated on the lithium foil, and the
light from a mercury lamp was irradiated onto the
alumina-evaporated PET side for 10 minutes to cure the
polymerizable monomer solution and adhere the lithium foil to the
SPE layer. As a result, a film laminate consisting of
copper/lithium/SPE/alumina-evaporated PET was obtained.
[0347] Then, the lithium cobaltate/alumina foil laminate electrode
produced in Example 23 was cut into a size of 12 mm.times.12 mm and
impregnated with the above-described thermopolymerizable monomer
solution, and the SPE side of the laminate obtained above from
which the alumina-evaporated PET was peeled off was laminated on
the lithium cobaltate side. The polymerizable monomer solution was
cured by heating at 60.degree. C. for one hour to adhere the SPE to
the lithium cobaltate. As a result, a film laminate consisting of
copper/lithium/SPE/lithium cobaltate/aluminum was prepared.
[0348] The edge part of the laminate was sealed with an epoxy resin
to obtain a lithium/SPE/lithium cobaltate secondary battery.
[0349] FIG. 11 shows a schematic cross section of the battery thus
obtained.
[0350] The battery was subjected to repeated charging/discharging
at a working voltage of from 2.0 to 4.2 V and a current of 0.2 mA.
As a result, the maximum discharge capacity was 1.8 mAh and the
cyclelife until the capacity was reduced to 50% was150 cycles.
Example 29
[0351] Production of Li ion secondary battery:
[0352] In a glove box under an argon atmosphere, the
graphite/copper foil laminate electrode produced in Example 26 was
cut into a size of 12 mm.times.12 mm. After covering the periphery
of about 1 mm from four edges on the graphite side by a 5
.mu.m-thick polyimide film as a spacer, the laminate was
impregnated with the photopolymerizable monomer solution prepared
in Example 24. Then, the film laminate produced in Example 2 was
cut into a size of 12 mm.times.12 mm, the polypropylene film layer
was peeled therefrom, the SPE layer was laminated on the graphite
layer, and the light from a mercury lamp was irradiated onto the
alumina-evaporated PET side for 10 minutes to cure the
polymerizable monomer solution and adhere the graphite to the SPE
layer. As a result, a film laminate consisting of
copper/graphite/SPE/alumina-evaporated PET was obtained.
[0353] Then, the lithium cobaltate/aluminum foil laminate electrode
produced in Example 23 was cut into a size of 12 mm.times.12 mm and
impregnated with the thermopolymerizable monomer solution prepared
in Example 28, and the SPE side of the laminate obtained above from
which the alumina-evaporated PET was peeled off was laminated on
the lithium cobaltate side. The polymerizable monomer solution was
cured by heating at 60.degree. C. for one hour to adhere the SPE to
the lithium cobaltatel. As a result, a film laminate consisting of
copper/graphite/SPE/lithium cobaltate/aluminum was prepared.
[0354] The edge part of the laminate was sealed with an epoxy resin
to obtain a graphite/SPE/lithium cobaltate secondary battery
similar to that shown in FIG. 11.
[0355] The battery was subjected to repeated charging/discharging
at a working voltage of from 2.0 to 4.2 V and a current of 0.2 mA.
As a result, the maximum discharge capacity was 1.7 mAh and the
cycle life until the capacity was reduced to 50% was 410 cyles.
Example 30
[0356] Production of Li ion secondary battery:
[0357] In a glove box under an argon atmosphere, the
graphite/copper foil laminate electrode produced in Example 26 was
cut into a size of 12 mm.times.12 mm. After covering the periphery
of about 1 mm from four edges on the graphite side by a polyimide
film (5 .mu.m-thick) as a spacer, the laminate was impregnated with
the thermopolymerizable monomer solution prepared in Example 28.
Then, the film laminate consisting of aluminum foil/lithium
cobaltate/SPE/polypropylene produced in Example 24 was cut into a
size of 12 mm.times.12 mm, the polypropylene film layer was peeled
therefrom, the SPE layer was laminated on the graphite, and the
polymerizable monomer solution was cured by heating at 60.degree.
C. for one hour to adhere the SPE to the graphite layer. As a
result, a film laminate consisting of copper/graphite/SPE/lithium
cobaltate/aluminum was obtained.
[0358] The edge part of the laminate was sealed with an epoxy resin
to obtain a graphite/SPE/lithium cobaltate secondary battery
similar to that shown in FIG. 11.
[0359] The battery was subjected to repeated charging/discharging
at a working voltage of from 2.0 to 4.2 V and a current of 0.2
.mu.mA. As a result, the maximum discharge capacity was 1.6 mAh and
the cycle life until the capacity was reduced to 50% was 430
cycles.
Example 31
[0360] Production of Li ion secondary battery:
[0361] In a glove box under an argon atmosphere, the film laminate
consisting of copper foil/graphite/SPE/polypropylene produced in
Example 27 was cut into a size of 12 mm.times.12 mm, the
polypropylene film layer was peeled therefrom, and the
thermopolymerizable monomer solution prepared in Example 28 was
thinly (about 1 .mu.m) coated on the SPE layer surface. Then, a
film laminate consisting of aluminum foil/lithium
cobaltate/SPE/polypropylene prepared in Example 24 was cut into a
size of 12 mm.times.12 mm, the polypropylene film layer was peeled
therefrom, the SPE layer was laminated on the above solid polymer
electrolyte coated with the thermopolymerizable monomer, and the
polymerizable monomer solution was cured by heating at 60.degree.
C. for one hour to adhere the SPE layers with each other. As a
result, a film laminate consisting of copper/graphite/SPE/lithium
cobaltate/aluminum was prepared.
[0362] The edge part of the laminate was sealed with an epoxy resin
to obtain a graphite/SPE/lithium cobaltate secondary battery. FIG.
12 shows a schematic cross section of the battery thus
obtained.
[0363] The battery was subjected to repeated charging/discharging
at a working voltage of from 2.0 to 4.2 V and a current of 0.2 mA.
As a result, the maximum discharge capacity was 1.6 mAh and the
cycle life until the capacity was reduced to 50% was 380
cycles.
Example 32
[0364] Production of activated carbon/SUS laminate electrode:
[0365] To a 9.0:1.0 (by weight) mixture of coconut husk activated
carbon and polyvinylidene fluoride (PVdF), excess
N-methyl-pyrrolidone was added to obtain a gelled composition. The
composition thus obtained was coated on a stainless steel (SUS)
foil in a size of 10 cm.times.10 cm to a thickness of about 150
.mu.m. The coating was vacuum dried at about 100.degree. C. for 10
hours to obtain an activated carbon/SUS laminate electrode.
Example 33
[0366] Under an argon atmosphere, 1.50 g of Compound 8, 4.0 g of
propylene carbonate (PC), 0.35 g of LiBF.sub.4 and 0.02 g of
Irgacure 500 (produced by Ciba Geigy AG) were well mixed to obtain
a photopolymerizable monomer solution.
[0367] The resulting photopolymerizable monomer solution was, under
a nitrogen atmosphere, absorbed into the activated carbon of the
activated carbon/SUS laminate electrode produced in Example 32 and
further coated thereon by means of a coater to a thickness of 30
.mu.m. Then, the light from a mercury lamp was irradiated onto the
laminate for 1 minute to form a SPE layer. Thereafter, on the SPE
layer, a polypropylene film (30 .mu.m-thick) was superposed and
then irradiated with a mercury lamp for 10 minutes to obtain a film
laminate consisting of SUS foil/activated
carbon/SPE/polypropylene.
[0368] The water content of the SPE layer of the laminate was 180
ppm (according to Karl Fischer's method). The laminate was stored
in a thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. Then, the water content of the SPE
layer was 200 ppm and had hardly increased from its value prior to
storage.
[0369] The polypropylene film was peeled off from the laminate and
in the same manner as above, the laminate was stored in a
thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer increased to 5,000 ppm.
Example 34
[0370] Under an argon atmosphere, 1.50 g of Compound 3, 3.0 g of
propylene carbonate (PC), 0.30 g of LiBF.sub.4 and 0.02 g of
Irgacure 500 (produced by Ciba Geigy AG) were well mixed to obtain
a photopolymerizable monomer solution.
[0371] The resulting photopolymerizable monomer solution was coated
on an alumina layer of a PET film (50 .mu.m-thick) having
vapor-deposited thereon a 500 .ANG.-thick alumina layer, under a
nitrogen atmosphere by means of a coater to a thickness of 30 .mu.m
and cured by irradiating with a mercury lamp for 10 minutes to
obtain a transparent SPE layer. Furthermore, on the SPE layer, a
polypropylene film (30 .mu.m-thick) was laminated under a nitrogen
atmosphere by means of nip rolls to obtain a film laminate
consisting of PET/alumina/SPE/polypropylene.
[0372] The ion conductivity at 25.degree. C. of the SPE layer was
measured by an impedance method and determined to be
2.times.10.sup.-3 S/cm.
[0373] The water content of the SPE layer was 180 ppm (according to
Karl Fischer's method). The laminate was stored in a thermostatic
chamber at a temperature of 23.degree. C. and a humidity of 60% RH
for one hour. Then, the water content of the SPE layer was 200 ppm
and had hardly increased from its value prior to storage. The ion
conductivity did not change and was 2.times.10.sup.-3 S/cm.
[0374] The polypropylene film and/or PET/alumina layer as an upper
or lower layer could be peeled off from the laminate and the SPE
layer could be easily laminated on another substrate such as an
electrode.
Example 35
[0375] Production of electrical double layer capacitor:
[0376] Under an argon atmosphere, 1.50 g of Compound 8, 4.0 g of
propylene carbonate (PC), 0.35 g of LiBF.sub.4 and 0.001 g of AIBN
were well mixed to obtain a thermopolymerizable monomer
solution.
[0377] In a glove box under an argon atmosphere, the activated
carbon/SUS laminate electrode produced in the same manner as in
Example 32 was cut into a size of 12 mm.times.12 mm and impregnated
with the photopolymerizable monomer solution prepared in Example
33. Then, the film laminate prepared in Example 34 was cut into a
size of 12 mm.times.12 mm, the polypropylene film layer was peeled
therefrom, the SPE layer was laminated on the activated carbon, and
the polymerizable monomer solution was cured by irradiating with a
mercury lamp for 10 minutes from the alumina-evaporated PET side to
adhere the activated carbon to the SPE layer. As a result, a film
laminate consisting of SUS/activated carbon/SPE/alumina-evaporated
PET was obtained.
[0378] The activated carbon/SUS laminate electrode produced in the
same manner as in Example 32 was cut into a size of 12 mm.times.12
mm and impregnated with the above thermopolymerizable monomer
solution, and the activated carbon side was laminated on the SPE
side of the SUS/activated carbon/SPE/alumina-evaporated PET
laminate from which the alumina-evaporated PET layer was peeled
off. Then, the polymerizable monomer solution was cured by heating
at 60.degree. C. for one hour to produce a film laminate consisting
of SUS/activated carbon/SPE/activated carbon/SUS.
[0379] The edge part of the laminate was sealed with an epoxy resin
to obtain an electrical double layer capacitor.
[0380] FIG. 13 shows a schematic cross section of the electrical
double layer capacitor thus obtained.
[0381] The capacitor was charged/discharged at a working voltage of
from 0 to 2.0 V and a current of 0.1 mA. As a result, the maximum
capacity was 160 mF. Furthermore, even after repeating the
charging/discharging 50 times under the above-described conditions,
the capacity was hardly changed.
Example 36
[0382] Production of solid electrical double layer capacitor:
[0383] In a glove box under an argon atmosphere, the film laminate
consisting of SUS foil/activated carbon/SPE/polypropylene produced
in Example 33 was cut into two sheets in a size of 12 mm.times.12
mm. The polypropylene film layer of one laminate was peeled off and
on a surface of the SPE layer, the thermopolymerizable monomer
solution prepared in Example 35 was thinly (about 1 .mu.m) coated.
From the other film laminate consisting of SUS foil/activated
carbon/SPE/polypropylene, the polypropylene film layer was peeled
off and the SPE layer was laminated on the SPE coated with the
thermopolymerizable monomer. Then, the polymerizable monomer
solution was cured by heating at 60.degree. C. for one hour to
adhere the SPE layers to each other. As a result, a film laminate
consisting of SUS/activated carbon/SPE/activated carbon/SUS was
prepared.
[0384] The edge part of the laminate was sealed with an epoxy resin
to obtain an electrical double layer capacitor.
[0385] FIG. 13 shows a schematic cross section of the electrical
double layer capacitor thus obtained.
[0386] The capacitor was charged/discharged at a working voltage of
from 0 to 2.0 V and a current of 0.1 mA. As a result, the maximum
capacity was 170 mF. Furthermore, even after repeating the
charging/discharging 50 times under the above-described conditions,
the capacity was hardly changed. EXAMPLE 37
[0387] Preparation of tungsten trioxide (WO.sub.3) electrochromic
layer:
[0388] An ITO (indium tin oxide) glass produced by Matsuzaki Shinku
KK was cut into a size of 12 mm.times.12 mm, the edge was covered,
and on the resulting electrode having an ITO exposure area of 10
mm.times.10 mm, WO.sub.3 was vacuum evaporated using a tantalum as
a boat member by a resistance heating method at from 10.sup.-5 to
10.sup.-6 Torr. The film thus obtained had a thickness of about
1,000 .ANG. and a density of about 5 g/cm.sup.3.
Example 38
[0389] Preparation of electrolytically polymerized polyaniline
film:
[0390] On an electrode of an ITO glass produced by Matsuzaki Shinku
KK and cut into a size of 12 mm.times.12 mm, potential scanning was
repeatedly performed in a 1M aqueous hydrochloric acid solution
containing 0.5M aniline as an electrolytic solution with an ITO
glass of 20 mm.times.20 mm as a counter electrode in the range of
from -0.2 to 0.8 V vs. SCE at a scanning rate of 0.2 V/sec, to form
a green and doped, electrically polymerized polyaniline thin film
of about 5,000 .ANG. on the ITO glass. Then, the polyaniline thin
film was undoped with aqueous ammonia, thoroughly washed with
distilled water, and dipped in an aqueous hydrazine solution to
obtain a colorless undoped film. The film was vacuum dried at
100.degree. C. for about 3 hours.
Example 39
[0391] Production of electrochromic display (ECD):
[0392] In a glove box under an argon atmosphere, the polyaniline
thin film/ITO electrode produced in Example 38 was impregnated with
the photopolymerizable monomer solution prepared in Example 24.
Then the film laminate prepared in Example 2 was cut out into a
size of 12 mm.times.12 mm, the polypropylene film layer was peeled
off, the SPE layer was laminated onto the polyaniline thin film,
and the light from a mercury lamp was irradiated onto the laminate
for 10 minutes from the alumina-evaporated PET side to cure the
polymerizable monomer solution and adhere the polyaniline to the
SPE layer. As a result, a film laminate consisting of
ITO/polyaniline/SPE/alumina-evaporated PET was obtained.
[0393] Then, the WO.sub.3/ITO electrode produced in Example 37 was
impregnated with the thermopolymerizable monomer solution prepared
in Example 28 and the SPE side of the laminate from which the
alumina-evaporated PET was peeled off was laminated to the WO.sub.3
side. Thereafter, the polymerizable monomer was cured by heating at
60.degree. C. for one hour to adhere the SPE to WO.sub.3. A film
laminate consisting of ITO/polyaniline/SPE/WO.sub.3/ITO was thus
obtained.
[0394] The edge part of the laminate was sealed with an epoxy resin
to obtain an ECD consisting of polyaniline/SPE/WO.sub.3.
[0395] FIG. 14 shows a schematic cross section of the ECD thus
obtained.
[0396] The ECD was subjected to repeated coloration/decolorization
driving at a working voltage of from -2.0 to 2.0 V and an injection
quantity of electricity of 6 mC/cm.sup.2. Then, a deep blue/light
blue electrochromism was observed. The speed of the response was
about 300 msec. Furthermore, even after repeating the driving 100
times under the above-described conditions, the color tone and the
speed of response were not changed.
Example 40
[0397] Under an argon atmosphere, 1.50 g of Compound 6, 2.0 g of
.gamma.-butyrolactone (GBL), 2.0 g of ethylene carbonate (EC), 0.2
g of NaBF.sub.4, 0.2 g of NaI and 0.02 g of Irgacure 500 (produced
by Ciba Geigy AG) were well mixed to obtain a photopolymerizable
monomer solution.
[0398] The resulting photopolymerizable monomer solution was coated
on an alumina layer of a PET film (50 .mu.m-thick) having
vapor-deposited thereon a 500 .ANG.-thick alumina layer, under a
nitrogen atmosphere by means of a coater to a thickness of 30 .mu.m
and cured by irradiating with a mercury lamp for 10 minutes to
obtain a transparent SPE layer. Furthermore, on the SPE layer, a
polypropylene film (30 .mu.m-thick) was laminated under a nitrogen
atmosphere by means of nip rolls to obtain a film laminate
consisting of PET/alumina/SPE/polypropylene.
[0399] The ion conductivity at 25.degree. C. of the SPE layer was
measured by an impedance method and found to be 5.times.10.sup.-3
S/cm. The water content of the SPE layer was 500 ppm (according to
Karl Fischer's method). The laminate was stored in a thermostatic
chamber at a temperature of 23.degree. C. and a humidity of 60% RH
for one hour. Then, the water content of the SPE layer was 500 ppm
and had hardly increased from its value prior to storage. The ion
conductivity did not change and was 5.times.10.sup.-3 S/cm.
[0400] The polypropylene and/or PET film as an upper or lower layer
could be peeled off from the laminate and the SPE layer could be
easily laminated on another substrate such as an electrode.
Example 41
[0401] Production of Cd (Se, Te) photoelectrode:
[0402] According to the method reported in Journal of
Electrochemical Society, Vol. 132, page 1077 (1985), a Cd (Se, Te)
photoelectrode having a thickness of about 1 .mu.m was produced by
electrodepositing from an aqueous sulfuric solution of CdSO.sub.4,
SeO.sub.2 or TeO.sub.2 on a titanium electrode having a dimension
of 12 mm.times.12 mm.
Example 42
[0403] Production and evaluation of wet-type solar cell
(photoelectrochemical solar cell):
[0404] The periphery of about 1 mm from four edges of the Cd (Se,
Te)/Ti photoelectrode produced above was covered by a 5 .mu.m-thick
polyimide film, and the photopolymerizable monomer solution
prepared in Example 40 was coated on the Cd (Se, Te) thin film.
Then, the film laminate produced in Example 40 was cut into a size
of 12 mm.times.12 mm and the polypropylene film layer was peeled
off. The SPE layer was laminated on the Cd (Se, Te) thin film and
the light from a mercury lamp was irradiated onto the laminate for
10 minutes from the alumina-evaporated PET side to cure the
polymerizable monomer solution and adhere the Cd (Se, Te) thin film
to the SPE layer. As a result, a film laminate consisting of Ti/Cd
(Se, Te)/SPE/alumina-evaporated PET was obtained.
[0405] Then, the photopolymerizable monomer solution prepared in
Example 40 was coated on an ITO electrode (12 mm.times.12 mm) and
the SPE side of the laminate obtained above from which the
alumina-evaporated PET was peeled off was laminated to the coated
surface of the ITO electrode. The light from a mercury lamp was
irradiated onto the laminate for 10 minutes from the ITO side to
cure the photopolymerizable monomer solution and adhere the ITO to
the SPE layer. As a result, a film laminate consisting of Ti/Cd
(Se, Te)/SPE/ITO was obtained.
[0406] The edge part of the laminate was sealed with an epoxy resin
to obtain a Cd (Se, Te)/SPE/ITO wet-type solar cell
(photoelectrochemical solar cell).
[0407] FIG. 15 shows a schematic cross section of the wet-type
solar cell (photoelectrochemical solar cell) thus obtained.
[0408] When a tungsten-halogen lamp of 500 W used as a light source
was irradiated onto the solar cell for one hour, the open circuit
voltage was 0.4 V and in a closed circuit, the current was 0.1
mA/cm.sup.2. This was observed for 30 minutes or more, which
indicates that the cell was working as a photoelectric cell.
Example 43
[0409] On a PET film, ITO was evaporated to a thickness of 1,000
.ANG. and the ITO was soldered with an SUS steel foil as a terminal
to obtain a film laminate (12 mm.times.12 mm; thickness: 30 .mu.m)
consisting of ITO layer/PET layer. On the ITO layer of the
laminate, the polymerizable monomer solution prepared in Example 9
was coated under a nitrogen atmosphere by means of a coater to a
thickness of 30 .mu.m and the light from a mercury lamp was
irradiated onto the laminate for 1 minute to form a SPE layer. On
the SPE layer, a polypropylene film (30 .mu.m-thick) was laminated
and the light from a mercury lamp was further irradiated thereon
for 10 minutes to obtain a film laminate consisting of PET/ITO
(with SUS terminal)/SPE/polypropylene. The ion conductivity at
25.degree. C. of the SPE layer of the laminate was measured by an
impedance method and found to be 1.times.10.sup.-4 S/cm. The water
content of the SPE layer was 230 ppm (according to Karl Fischer's
method). The laminate was stored in a thermostatic chamber at a
temperature of 23.degree. C. and a humidity of 60% RH for one hour.
Then, the water content of the SPE layer was 230 ppm which was the
same as its value prior to storage. The ion conductivity was
unchanged and was 1.times.10.sup.-4 S/cm.
[0410] The polypropylene film layer was peeled off from the
laminate and in the same manner as above, the laminate was stored
in a thermostatic chamber at a temperature of 23.degree. C. and a
humidity of 60% RH for one hour. As a result, the water content of
the SPE layer was increased to 800 ppm. The ion conductivity did
not change and was 1.times.10.sup.-4 S/cm.
[0411] The polyethylene film and/or polypropylene film as an upper
or lower layer could be peeled off from the laminate and the SPE
layer could be easily laminated on another substrate such as an
electrode.
[0412] The polypropylene film layer was peeled off from the
laminate and on the SPE layer of the laminate from which the
polypropylene layer was peeled off, the photoelectrode prepared in
the same manner as in Example 41 was laminated in the same manner
as in Example 42. As a result, a solar cell similar to that of
Example 42 was obtained.
Example 44
[0413] A silver paste was spray coated only on the edge surfaces
opposing to each other of a film laminate consisting of
polyethylene/SPE/polypropy- lene produced in the same manner as in
Example 9. Furthermore, a SUS steel-made lead wire was soldered on
the silver paste. The resistivity of the SPE portion between two
silver paste-coated surfaces was 3.times.10.sup.4
.OMEGA..multidot.cm. The laminate could be used as an electrically
conductive material of which the upside and down side each was
covered with an insulating backing (polyethylene or
polypropylene).
[0414] The ion conductive laminate of the present invention has an
ion conductive material layer having excellent ion conductivity at
high temperatures, at room temperature and at low temperatures, a
small water content and a homogenous thickness. Accordingly, the
inventive laminate is advantageously used in the production of
various electrochemical elements and electrochemical apparatuses
such as a secondary battery, an electrical double layer capacitor,
an electrochromic display element or apparatus, a photoelectric
cell and a solar cell. In particular, when the solid polymer
electrolyte (SPE) or polymer gel electrolyte (PGE) is used in
electrochemical elements or in electrochemical apparatuses, the
capability to process the electrolyte into a desired shape such as
a film, the homogeneity of the electrolyte in a laminating step,
and the shape stability of the electrolyte such as film thickness
and moisture absorption, all of which are problems related to
handling the electrolyte, are remarkably improved. Furthermore, the
laminate of the present invention is advantageous in the production
of various electrochemical elements and apparatuses. Namely, the
ion conductive material such as a SPE and PGE having a constant
quality can be stored in a state which allows for stable use at any
time. Furthermore, the electrolyte quality is consistently
excellent and the handling is very easy.
[0415] According to the production method of an electrochemical
element or electrochemical apparatus using the ion conductive
laminate of the present invention, an element or apparatus can be
obtained which can be used in layer form such as a film having a
homogenous thickness using a SPE or PGE having a very high quality
and a small water content. The production is stable, simple and
easy, and can be achieved at high yield, as compared with known
methods such as coating.
[0416] Furthermore, the ion conductive laminate of the present
invention can be used as an electrically conductive material for
preventing electrification or for the production of such a
material.
[0417] The ion conductive laminate of the present invention can be
formed into a layer material having any size and shape, and in
particular, into a homogeneous and high-quality layer material
(e.g., film, sheet, plate) having a very large area and/or length
and/or any thickness from ultrathin to bulky. This cannot be
achieved with other methods, and this excellent property is not
seen in conventional ion conductive materials. Thus, by using the
laminate of the present invention, various large-size
electrochemical elements and apparatuses described above, which
could not be achieved heretofore, can be produced.
[0418] While the invention has been described in detail and with
reference to specific embodiments thereof, it will be apparent to
one skilled in the art that various changes and modifications can
be made therein without departing from the spirit and scope
thereof.
* * * * *