U.S. patent application number 09/139374 was filed with the patent office on 2001-07-19 for sulfonylimide compounds.
This patent application is currently assigned to 3M INNOVATIVE PROPERTIES COMPANY. Invention is credited to FANTA, ALAN DAVID, HAMROCK, STEVEN JOSEPH, PHAM, PHAT TAN.
Application Number | 20010008736 09/139374 |
Document ID | / |
Family ID | 22486317 |
Filed Date | 2001-07-19 |
United States Patent
Application |
20010008736 |
Kind Code |
A1 |
FANTA, ALAN DAVID ; et
al. |
July 19, 2001 |
SULFONYLIMIDE COMPOUNDS
Abstract
Novel sulfonylimide and sulfonylmethide compounds are described
which are useful as conductive salts. Also described is the use of
the above compounds in salt form in battery electrolytes,
particular salts having mixed perfluorocarbon and hydrocarbon
groups or having all hydrocarbon groups. The above salts are less
expensive to produce and still exhibit excellent conductivity and
low corrosivity.
Inventors: |
FANTA, ALAN DAVID;
(MINNEAPOLIS, MN) ; PHAM, PHAT TAN; (LITTLE
CANADA, MN) ; HAMROCK, STEVEN JOSEPH; (ST PAUL,
MN) |
Correspondence
Address: |
DANIEL C SCHULTE
3M OFFICE OF INTELLECTUAL PROPERTY
COUNSEL
P O BOX 33427
ST PAUL
MN
551333427
|
Assignee: |
3M INNOVATIVE PROPERTIES
COMPANY
|
Family ID: |
22486317 |
Appl. No.: |
09/139374 |
Filed: |
August 25, 1998 |
Current U.S.
Class: |
429/307 ;
429/314; 429/316; 429/329; 429/347; 549/11; 549/468; 549/490;
564/102; 568/30 |
Current CPC
Class: |
Y02E 60/10 20130101;
H01M 10/0568 20130101; C08F 30/04 20130101; C07F 17/00 20130101;
C07D 291/00 20130101; H01M 10/052 20130101; C07D 291/08 20130101;
C07C 311/48 20130101; C07C 307/02 20130101; H01M 6/181 20130101;
C07D 285/00 20130101 |
Class at
Publication: |
429/307 ;
429/314; 429/316; 429/329; 429/347; 549/11; 564/102; 568/30;
549/468; 549/490 |
International
Class: |
H01M 006/18; H01M
006/16; H01M 010/40; C07C 313/00; C07D 341/00; C07D 409/00; C07D
495/00; C07C 315/00; C07D 307/50; C07D 307/93 |
Claims
We claim:
1. A compound of the
formulaN.sup.-(SO.sup.2XR.sub.p).sup.m(SO.sup.2R').su-
b.o1/nM.sup.n+wherein: m is 1 or 2 and m+o is 2; X is independently
O or N; p is 1 when X is O, and p is 2when X is N; R is each
independently a monovalent hydrocarbon group; two R groups when
taken together form a divalent hydrocarbon group joined to two X
atoms, in which the hydrocarbon groups are uninterrupted or
interrupted by a heteroatom; or two R groups when taken together
may form a three- to six-membered ring with a nitrogen atom, which
ring may be further interrupted by a heteroatom; R' is each
independently a hydrocarbon group or a straight or branched acyclic
fluoroalkyl group having from 1 to 12 carbon atoms, a cyclic
fluoroalkyl group having from 3 to 12 carbon atoms, or a
fluorocycloalkyl-fluoroalkyl group where the fluoroalkyl group has
from I to 4 carbon atoms, in which the fluoroalkyl and
fluorocycloalkyl groups are uninterrupted or interrupted by a
heteroatom; or an R group and an R' group when taken together may
form a ring, which ring may be further interrupted by a catenary
heteroatom; and M.sup.n+is a cation having a valence of n; with the
proviso that when m is 2, M.sup.n+is a metal or alkylammonium
cation of the formula R".sub.4N.sup.+, where R" is independently
alkyl having 1 to 4 carbon atoms.
2. A compound according to claim 1, wherein R is each independently
a straight or branched aliphatic group having 1 to 18 carbon atoms;
a cycloaliphatic group of 3 to 12 carbon atoms; a
cycloaliphatic-aliphatic group where the aliphatic group has 1 to 4
carbon atoms, in which the carbon chain of the aliphatic or
cycloaliphatic groups is uninterrupted or interrupted by a
heteroatom; an aryl, biaryl or aralkyl group, in which said alkyl
has 1 to 4 carbon atoms and aryl is unsubstituted or substituted by
alkyl of 1 to 4 carbon atoms, nitro, halo, trifluoromethyl or
cyano.
3. A compound according to claim 1, wherein two R groups form an
alkylene group, a 1,2-phenylene group, or a 1,1'-bis-phenylene
group joined to two X atoms.
4. A compound according to claim 1, wherein the heteroatom is
nitrogen, oxygen or sulfur.
5. A compound according to claim 1, wherein p is 2 and two R groups
form an alkylene group forming a 3- to 6-membered ring with the
nitrogen atom.
6. A compound according to claim 1, wherein p is 1 or 2 and o is 1
or 2, and both R and R' form an alkylene group of 2 or 3 carbon
atoms or a phenylene group joined at the 1,2-positions to form a
ring.
7. A compound according to claim 2, wherein R is a straight or
branched aliphatic group, a cycloaliphatic group, or an aryl
group.
8. A compound according to claim 1, wherein R is a member selected
from the group consisting of CH.sub.3-, C.sub.2H.sub.5-,
(CH.sub.3).sub.2CH--, (CH.sub.3).sub.3CCH.sub.2-, C.sub.8H.sub.17-,
C.sub.6H.sub.5-, C.sub.10H.sub.7-, H.sub.3CC.sub.6H.sub.4-,
O.sub.2NC.sub.6H.sub.4-, FC.sub.6H.sub.4-, NCC.sub.6H.sub.4-,
(CF.sub.3).sub.2C.sub.6H.sub.3-, CH.sub.2.dbd.CH.sub.2-,
CH.sub.2.dbd.CHCH.sub.2-, CH.sub.2.dbd.C(CH.sub.3- )--,
CH.sub.2.dbd.CHC(O)OC.sub.2H.sub.4-,
CH.sub.2.dbd.C(CH.sub.3)C(O)OC.s- ub.2H.sub.4-,
CH.sub.2.dbd.CH--C.sub.6H.sub.4-, HC.ident.CCH.sub.2-,
OCN(CH.sub.2).sub.6NH--, OCN--C.sub.6H.sub.4-, HOC.sub.2H4-,
HOCH.sub.2CH(OH)CH.sub.2-, H.sub.2NC.sub.2H.sub.4-,
(CH.sub.3O).sub.3SiC.sub.3H.sub.6-,
(CH.sub.3O).sub.2(CH.sub.3)SiC.sub.3H- .sub.6-, 13
9. A compound according to claim 1, wherein two R groups form a
member selected from the group consisting of --CH.sub.2CH.sub.2-,
--CH.sub.2CH(CH.sub.3)--, --CH.sub.2.dbd.CH--C.sub.6H.sub.4-,
14
10. A compound according to claim 1, wherein R' is a member
selected from the group consisting of CH.sub.3-, C.sub.2H.sub.5-,
(CH.sub.3).sub.2CH--, (CH.sub.3).sub.3CCH.sub.2-, C.sub.8H.sub.17-,
C.sub.6H.sub.5-, C.sub.10H.sub.7-, H.sub.3CC.sub.6H.sub.4-,
O.sub.2NC.sub.6H.sub.4-, FC.sub.6H.sub.4-, NCC.sub.6H.sub.4-,
(CF.sub.3).sub.2C.sub.6H.sub.3-, CH.sub.2.dbd.CH.sub.2-,
CH.sub.2.dbd.CH--CH.sub.2-, CH.sub.2.dbd.CHC(O)--,
CH.sub.2.dbd.C(CH.sub.3)C(O)--,
CH.sub.2.dbd.CHC(O)OC.sub.2H.sub.4-,
CH.sub.2.dbd.C(CH.sub.3)C(O)OC.sub.2- H.sub.4-,
CH.sub.2.dbd.CH--C.sub.6H.sub.4-, HC.ident.CCH.sub.2-,
OCN(CH.sub.2).sub.6NHC(O)--, OCN--C.sub.6H.sub.4-,
HOC.sub.2H.sub.4-, HOCH.sub.2CH(OH)CH.sub.2-,
H.sub.2NC.sub.2H.sub.4-, (CH.sub.3O).sub.3SiC.sub.3H.sub.6-,
(CH.sub.3O).sub.2(CH.sub.3)SiC.sub.3H- .sub.6-, 15
11. A compound according to claim 1, wherein R' is a member
selected from the group consisting of CF.sub.3-, C.sub.2F.sub.5-,
C.sub.4F.sub.9-, C.sub.8F.sub.17, (CF.sub.3).sub.2NC.sub.2F.sub.4-,
CF.sub.3OC.sub.2F.sub.4-, 16
12. A compound according to claim 1, wherein M.sup.n+is a cation
selected from the group consisting of an alkali metal; an alkaline
earth metal; a Group IIIA metal; a transition metal; a proton; an
ammonium cation of the formula R.sub.4N.sup.+; a sulfonium cation
of the formula R.sub.3S.sup.+; an iodonium cation of the formula
R.sub.2I.sup.+; and a phosphonium cation of the formula
R.sub.4P.sup.+; where R is independently alkyl having from 1 to 4
carbon atoms, aryl or hydrogen.
13. A compound according to claim 12, wherein the cation is an
alkali metal.
14. A compound according to claim 13, wherein the cation is
lithium.
15. A compound according to claim 1 and of the formula 17
16. A compound according to claim 1 and of the formula
[(CH.sub.3).sub.2CHOSO.sub.2].sub.2N.sup.-Li.sup.+.
17. A compound according to claim 1 and of the formula
[(CH.sub.3).sub.2NSO.sub.2](CF.sub.3SO.sub.2)N.sup.-Li.sup.+.
18. A compound according to claim 1 and of the formula 18
19. A compound according to claim 1 and of the formula
(C.sub.6H.sub.5)SO.sub.2N.sup.-Li.sup.+SO.sub.2N(CH.sub.3).sub.2.
20. A battery electrolyte comprising: (a) a salt of the formula
N.sup.-(SO.sub.2XR.sub.p).sub.m(SO.sub.2R').sub.o 1/nM.sup.n+
wherein: m is 1 or 2 and m+o is 2; X is independently O or N; p is
1 when X is O, and p is 2 when X is N; R is each independently a
monovalent hydrocarbon group; two R groups when taken together form
a divalent hydrocarbon group joined to two X atoms, in which the
hydrocarbon groups are uninterrupted or interrupted by a
heteroatom; or two R groups when taken together may form a three-
to six-membered ring with a nitrogen atom, which ring may be
further interrupted by a heteroatom; R' is each independently a
hydrocarbon group or a straight or branched acyclic fluoroalkyl
group having from 1 to 12 carbon atoms, a cyclic fluoroalkyl group
having from 3 to 12 carbon atoms, or a fluorocycloalkyl-fluoroalkyl
group where the fluoroalkyl group has from 1 to 4 carbon atoms, in
which the fluoroalkyl and fluorocycloalkylene groups are
uninterrupted or interrupted by a catenary heteroatom; or an R
group and an R' group when taken together may form a ring, which
ring may be further interrupted by a heteroatom; and M.sup.n+is a
cation having a valence of n; and (b) a matrix material.
21. The electrolyte of claim 20, wherein R is a straight or
branched aliphatic group having 1 to 18 carbon atoms; a
cycloaliphatic group of 3 to 12 carbon atoms; a
cycloaliphatic-aliphatic group where the aliphatic group has 1 to 4
carbon atoms, in which the carbon chain of the aliphatic or
cycloaliphatic groups is uninterrupted or interrupted by a
heteroatom, an aryl, biaryl or aralkyl group, in which said alkyl
has 1 to 4 carbon atoms, and aryl is unsubstituted or substituted
by alkyl of 1 to 4 carbon atoms, nitro, halo, trifluoromethyl or
cyano.
22. The electrolyte of claim 20, wherein two R groups form an
alkylene group or 1,2-phenylene group joined to two X atoms.
23. The electrolyte of claim 20, wherein R is a straight or
branched aliphatic group, a cycloaliphatic group, phenyl or
naphthyl, substituted by a reactive group, wherein the reactive
group is a polymerizable group.
24. The electrolyte of claim 20, wherein R is a member selected
from the group consisting of CH.sub.3-, C.sub.2H.sub.5-,
(CH.sub.3).sub.2CH, (CH.sub.3).sub.3CCH.sub.2-, C.sub.8H.sub.17-,
C.sub.6H.sub.5-, C.sub.10H.sub.7-, H.sub.3CC.sub.6H.sub.4-,
O.sub.2NC.sub.6H.sub.4-, FC.sub.6H.sub.4-, NCC.sub.6H.sub.4-,
(CF.sub.3).sub.2C.sub.6H.sub.3-, CH.sub.2.dbd.CH.sub.2-,
CH.sub.2.dbd.CH--CH.sub.2-, CH.sub.2.dbd.CHC(O)--,
CH.sub.2.dbd.C(CH.sub.3)C(O)--,
CH.sub.2.dbd.CHC(O)OC.sub.2H.sub.4-,
CH.sub.2.dbd.C(CH.sub.3)C(O)OC.sub.2- H.sub.4-, `CH.sub.2CH.sub.2-,
--CH.sub.2CH(CH.sub.3)--, --CH.sub.2.dbd.CH--C.sub.6H.sub.4-,
HC.ident. CCH.sub.2-, OCN(CH.sub.2).sub.6NHC(O)--,
OCN--C.sub.6H.sub.4-, HOC.sub.2H.sub.4-, HOCH.sub.2CH(OH)CH.sub.2-,
H.sub.2NC.sub.2H.sub.4-, (CH.sub.3O).sub.3SiC.sub.3H.sub.6-,
(CH.sub.3O).sub.2(CH.sub.3)SiC.sub.3H- .sub.6-, 19
25. The electrolyte of claim 20, wherein two R groups form a member
selected from the group consisting of --CH.sub.2CH.sub.2-,
--CH.sub.2CH(CH.sub.3)--, --CH.sub.2.dbd.CH--C.sub.6H.sub.4-,
20
26. The electrolyte of claim 20, wherein R' is a member selected
from the group consisting of CH.sub.3-, C.sub.2H.sub.5-,
(CH.sub.3).sub.2CH--, (CH.sub.3).sub.3CCH.sub.2-, C.sub.8H.sub.17-,
C.sub.6H.sub.5-, C.sub.10H.sub.7-, H.sub.3CC.sub.6H.sub.4-,
O.sub.2NC.sub.6H.sub.4-, FC.sub.6H.sub.4-, NCC.sub.6H.sub.4-,
(CF.sub.3).sub.2C.sub.6H.sub.3-, CH.sub.2.dbd.CH.sub.2-,
CH.sub.2.dbd.CH--CH.sub.2-, CH.sub.2.dbd.CHC(O)--,
CH.sub.2.dbd.C(CH.sub.3)C(O)--,
CH.sub.2.dbd.CHC(O)OC.sub.2H.sub.4-,
CH.sub.2.dbd.C(CH.sub.3)C(O)OC.sub.2- H.sub.4-,
CH.sub.2.dbd.CH--C.sub.6H.sub.4-, HC.ident.CCH.sub.2-,
OCN(CH.sub.2).sub.6NHC(O)--, OCN--C.sub.6H.sub.4-,
HOC.sub.2H.sub.4-, HOCH.sub.2CH(OH)CH.sub.2-,
H.sub.2NC.sub.2H.sub.4-, (CH.sub.3O).sub.3SiC.sub.3H.sub.6-,
(CH.sub.3O).sub.2(CH.sub.3)SiC.sub.3H- .sub.6-, 21CF.sub.3-,
C.sub.2F.sub.5-, C.sub.4F.sub.9-, C.sub.8F.sub.17,
(CF.sub.3).sub.2NC.sub.2F.sub.4-, CF.sub.3OC.sub.2F.sub.4-, 22
27. The electrolyte of claim 20, wherein M.sup.n+is lithium
cation.
28. The electrolyte of claim 20, which further comprises a one or
more conductive salts.
29. The electrolyte of claim 20, wherein the total salt
concentration in the matrix material is from about 0.1 M to about
2.0 M.
30. A battery comprising: at least one cathode, at least one anode,
and an electrolyte according to claim 20.
31. A homo- or copolymeric material comprising the reaction product
of one or more compounds of the formula
N.sup.-(SO.sub.2XR.sub.p).sub.m(SO.sub.2- R').sub.o
1/nM.sup.n+wherein: m is 1 or 2 and m+o is 2; X is independently O
or N; p is 1 when X is O, and p is 2 when X is N; R is each
independently a monovalent hydrocarbon group; two R groups when
taken together form a divalent hydrocarbon group joined to two X
atoms, in which the hydrocarbon groups are uninterrupted or
interrupted by a heteroatom; or two R groups when taken together
may form a three- to six-membered ring with a nitrogen atom, which
ring may be further interrupted by a heteroatom; R' is each
independently a hydrocarbon group or a straight or branched acyclic
fluoroalkyl group having from 1 to 12 carbon atoms, a cyclic
fluoroalkyl group having from 3 to 12 carbon atoms, or a
fluorocycloalkyl-fluoroalkyl group where the fluoroalkyl group has
from 1 to 4 carbon atoms, in which the fluoroalkyl and
fluorocycloalkyl groups are uninterrupted or interrupted by a
heteroatom; or an R group and an R' group when taken together may
form a ring, which ring may be further interrupted by a heteroatom;
wherein R or R' contain a polymerizable group; and M.sup.n+is a
cation having a valence of n.
32. The material of claim 31, wherein the polymerizable group is an
olefinic unsaturated group, an epoxide group, an isocyanato group
or a mixture thereof.
33. The material of claim 32, wherein the olefinic unsaturated
group is a vinyl, allyl, acrylyl, methacrylyl group or a mixture
thereof.
34. The material of claim 31, wherein R is a straight or branched
aliphatic group, a cycloaliphatic group, phenyl or naphthyl
substituted by a polymerizable group.
35. The material of claim 34, wherein the polymerizable group is an
olefinic unsaturated group, an epoxide group or an isocyanato
group.
36. The material of claim 35, wherein the olefinic unsaturated
group is a vinyl, allyl, acrylyl or methacrylyl group.
Description
FIELD OF THE INVENTION
[0001] This invention relates to sulfonylimide conductive salts
having mixed fluorocarbon and hydrocarbon groups or having all
hydrocarbon groups, and the use thereof in electrolytes for
electrochemical cells, such as lithium batteries.
BACKGROUND
[0002] Industry is continually searching for novel compounds which
can provide ionic conductivity when dissolved or dispersed in other
materials. These compounds often find use, for example, as
conductivity additives or enhancers, as cationic polymerization
initiators or catalysts, as anti-static additives, as
electrochemical sensors, and as surfactants. Such compounds are
especially useful when employed in combination with other materials
to form electrolytes to conduct electrical charge, for example,
when used in electrochemical cells and devices such as batteries,
fuel cells, electrochromic devices, capacitors, and
supercapacitors.
[0003] With respect to the specific application of electrolyte
compounds in electrochemical cells and devices, there is both a
current and projected future demand for high energy density,
lightweight, rechargeable power sources for use in automotive,
industrial and consumer markets. Many of these needs can be met by
lithium-ion battery technology, which requires the use of
electrolytic salts dissolved in a non-aqueous solvent or polymer to
act as an electrolyte. This electrolyte solution acts as the medium
through which ionic conduction can occur between electrodes,
providing charge balance within an electrochemical cell such as a
battery.
[0004] Of course, new electrolytic compounds must exhibit specific
chemical and physical properties to be useful in electrochemical
cells and devices. Of primary importance, the compounds must
exhibit good ionic conductivity and should be thermally and
electrochemically stable. Additionally, the compounds must also
exhibit good solubility at high concentration in common electrolyte
solvents and/or polymers; they should exhibit inertness to other
battery components (e.g., not cause corrosion of electrodes or
current collectors); they should be relatively non-toxic; they
should have acceptable environmental impact, and preferably they
should be able to be produced at an economically feasible price. In
the case of secondary (i.e., rechargeable) batteries, the compounds
should exhibit good cycling behavior at room temperature and
elevated temperature and should produce electrochemical cells that
can be operated and maintained with minimal concerns for safety
(e.g., explosions caused by thermal runaway).
[0005] There are currently only a small number electrolytic
compounds known to be suitable for use in lithium-ion batteries;
all are lithium salts and all have identifiable drawbacks. The most
common electrolyte compound is LiPF.sub.6, which exhibits good
conductivity and corrosion resistance, but is thermally and
hydrolytically unstable, decomposing to liberate fluoride ion which
is detrimental to cell performance. Other compounds having
potential uses in lithium electrolytes include LiAsF.sub.6 (toxic),
LiBF.sub.4 (relatively poor conductivity, thermally and
hydrolytically unstable), and LiClO.sub.4 (thermally unstable,
potentially explosive). There are also a number of known
organofluorine lithium compounds, but each of these has its own
individual shortcomings. Molecules like LiOSO.sub.2CF.sub.3 and
LiN(SO.sub.2CF.sub.3).sub.2 are thermally very stable but can be
corrosive to aluminum current collectors at the operative voltage
of a lithium ion cell, and LiC(SO.sub.2CF.sub.3).sub.3 is very
expensive to prepare.
[0006] There is a continuing need for new electrolyte compounds
which can perform at useful conductivity levels, and that are
easily handled and produced at a reasonable cost.
SUMMARY OF THE INVENTION
[0007] Conductive ionic compounds have been discovered that are
lower cost alternatives to the relatively expensive perfluorinated
sulfonates, sulfonylimides and sulfonylmethides now commercially
used in electrochemical cells such as lithium batteries, fuel
cells, capacitors, supercapacitors and electrochromic windows.
These ionic compounds are analogous to perfluoroalkanesulfonylimide
compounds in which some or all of the perfluoroalkyl groups have
been replaced with oxygen or nitrogen heteroatoms attached to
fluorine-free organic groups. By having part or even all of the
expensive perfluoroalkyl groups replaced, the compounds of this
invention can be made at a lower cost per pound and, having lower
molecular weights, can be used at lower weight concentrations in
electrolytes to produce a given molarity solution. Nonetheless,
these relatively inexpensive compounds exhibit good conductivity
and low corrosivity.
[0008] The present invention includes sulfonylimide compounds which
are particularly useful as conductive salts in battery
electrolytes.
[0009] In one aspect, the present invention includes novel salts of
the Formula I:
N.sup.-(SO.sub.2XR.sub.p).sub.m(SO.sub.2R').sub.o1/nM.sup.n+
[0010] wherein:
[0011] m is 1 or 2 and m+o is 2;
[0012] X is independently O or N;
[0013] p is 1 when X is O, and p is 2 when X is N;
[0014] R is each independently a monovalent hydrocarbon group; two
R groups when taken together form a divalent hydrocarbon group,
e.g. an alkylene group or a 1,2-phenylene group, joined to two X
atoms, in which the hydrocarbon groups are uninterrupted or
interrupted by a heteroatom; or two R groups when taken together
may form a three- to six-membered ring with a nitrogen atom, which
ring may be further interrupted by a heteroatom;
[0015] R' is a hydrocarbon group or a straight or branched acyclic
fluoroalkyl group having from 1 to 12 carbon atoms, a cyclic
fluoroalkyl group having from 3 to 12 carbon atoms, or a
fluorocycloalkyl-fluoroalkyl group where the fluoroalkyl group has
from 1 to 4 carbon atoms, in which the fluoroalkyl and
fluorocycloalkyl groups are uninterrupted or interrupted by a
heteroatom; or an R group and an R' group when taken together may
form a ring, which ring may be further interrupted by a heteroatom;
and
[0016] M.sup.n+is a cation having a valence of n;
[0017] with the proviso that when m is 2, M.sup.n+is a metal or
alkylammonium cation of the formula R".sub.4N.sup.+, where R" is
independently alkyl having 1 to 4 carbon atoms.
[0018] A second aspect of the present invention includes an
electrolyte for use in electrochemical cells containing:
[0019] (a) a salt of the Formula I,
N.sup.-(SO.sub.2XR.sub.p).sub.m(SO.sub- .2R').sub.o1/nM.sup.n+
[0020] wherein:
[0021] m is 1 or 2 and m+o is 2;
[0022] X is independently O or N;
[0023] p is 1 when X is O, and p is 2 when X is N;
[0024] R is each independently a monovalent hydrocarbon group; two
R groups when taken together form a divalent hydrocarbon group,
e.g. an alkylene group or a 1,2-phenylene group, joined to two X
atoms, in which the hydrocarbon groups are uninterrupted or
interrupted by a heteroatom; or two R groups when taken together
may form a three- to six-membered ring with a nitrogen atom, which
ring may be further interrupted by a heteroatom;
[0025] R' is a hydrocarbon group or a straight or branched acyclic
fluoroalkyl group having from 1 to 12 carbon atoms, a cyclic
fluoroalkyl group having from 3 to 12 carbon atoms, or a
fluorocycloalkyl-fluoroalkyl group where the fluoroalkyl group has
from 1 to 4 carbon atoms, in which the fluoroalkyl and
fluorocycloalkyl groups are uninterrupted or interrupted by a
heteroatom; or an R group and an R' group when taken together may
form a ring, which ring may be further interrupted by a heteroatom;
and
[0026] M.sup.n+is a cation having a valence of n; and
[0027] (b) a matrix material.
[0028] A third aspect of the present invention includes a battery
having at least one cathode, at least one anode and an electrolyte
as defined above.
DETAILED DESCRIPTION OF THE INVENTION
[0029] Throughout this application the following definitions
apply:
[0030] "Battery" includes all electrical energy storage devices,
including capacitors, electrochromic devices, and electrochemical
cells.
[0031] "Macromolecular material" refers to a homopolymer,
copolymer, or combination thereof, which may or may not be
cross-linked and/or plasticized.
[0032] "Gel" refers to a macromolecular material swollen with a
liquid.
[0033] "Matrix" or "matrix material" refers to a medium (e.g., a
solid, liquid, gel or plasticized polymer) in which salts according
to Formula I may be dissolved or dispersed to form an ionically
conductive electrolyte.
[0034] Voltages specified refer to electrical potential differences
between a positive electrode measured relative to a
Li/Li.sup.+reference electrode, except where otherwise noted.
[0035] The term "R'" appearing in the Formula and throughout the
specification can be a hydrocarbon group as defined below or a
fluorocarbon group containing at least one carbon atom in a
skeletal chain, such chain may be monovalent or divalent, branched
or cyclic. The skeletal chain of carbon atoms can be interrupted by
heteromoieties, such as divalent oxygen or trivalent nitrogen atoms
each of which is bonded only to carbon atoms, or hexavalent sulfur
atoms, each of which may be bonded to carbon, fluorine, or oxygen
atoms, but preferably where such heteromoieties are present, such
skeletal chain does not contain more than one said heteromoiety for
every two carbon atoms.
[0036] A fluorocarbon group may be either a partially or fully
fluorinated (i.e., perfluorinated) hydrocarbon chain. A partially
fluorinated hydrocarbon chain exists where only a portion of the
hydrogen atoms in the hydrocarbon has been replaced by fluorine
atoms. In a fully fluorinated or perfluorinated hydrocarbon chain,
essentially all of the hydrogen atoms, e.g. at least 90%, attached
to carbon have been replaced by fluorine. Thus, the non-skeletal
valence bonds are preferably carbon-to-fluorine bonds. However, an
occasional carbon bonded hydrogen atom, bromine atom or chlorine
atom may be present in a fully fluorinated hydrocarbon chain.
[0037] The total number of carbon atoms in a fluorocarbon group can
vary and be, for example, 1 to 12, preferably 1 to 8, more
preferably 1 to 4. Where the group is or contains a cyclic
structure, such structure preferably has 5 or 6 ring members, one
or two of which can be said heteromoieties, e.g., oxygen and/or
nitrogen.
[0038] A "hydrocarbon group" refers to a monovalent or divalent
straight or branched aliphatic group, a cycloaliphatic group, a
cycloaliphatic-aliphatic group, or an aryl, biaryl or aralkyl
group. These groups are further defined below.
[0039] "A straight or branched aliphatic group" refers to a
hydrocarbon radical which is either in the form of a straight or
branched chain and, in this case, ranging from 1 to 18 carbon atoms
or as otherwise designated. A preferred embodiment includes alkyl
straight or branched chain from 1 to 8 carbon atoms.
[0040] "Cycloaliphatic group" is a cyclic group having from 3 to 12
carbon atoms and refers to a cyclic saturated group. Thus, the
group includes, for example, cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, and the like.
[0041] The term "aryl" refers to a substituted or unsubstituted
aromatic or heteroaromatic hydrocarbon such as, for example,
phenyl, naphthyl, thienyl, pyridyl, pyrrolyl, and furyl. Preferred
is a phenyl or naphthyl group that is unsubstituted or substituted
by well recognized aromatic substituents such as, for example,
alkyl of 1-4 carbon atoms, nitro, halo, trifluoromethyl or cyano.
The phenyl or naphthyl group may be substituted by another phenyl
or naphthyl group and then form a biaryl group, e.g. a biphenyl
group. The phenyl or naphthyl group may further be substituted by a
"reactive group" defined below. Particularly preferred aromatic
groups include C.sub.6H.sub.5-, C.sub.10H.sub.7-,
CH.sub.3C.sub.6H.sub.4-, O.sub.2NC.sub.6H.sub.4-, FC.sub.6H.sub.4-,
(CF.sub.3).sub.2C.sub.6H.sub.3-, and NCC.sub.6H.sub.4-.
Particularly preferred divalent aromatic groups formed by two R
groups include 1
[0042] The term "reactive group" includes any group capable of
reacting with itself or with other groups. For example, R and R'
can contain a polymerizable group such as an olefinically
unsaturated group (e.g., acrylate or allyl), an epoxide group, an
isocyanato group and the like that would allow the sulfonylimide or
sulfonylmethide to react with other reactive compounds, including
other molecules of the same salt or molecules of a different
reactive or polymerizable compound, via grafting or polymerization
(cationic, anionic or free radical mechanism) to form a homopolymer
or a copolymer. Such a homopolymer or copolymer material would be
useful in electrolytes, particularly as single ion conductors.
Suitable reactive groups may be chosen from those groups containing
olefinic unsaturated groups (e.g., vinyl, allyl, vinylbenzyl,
acryloyl or methacryloyl groups) or from those groups containing
reactive heterocyclic ring structures (e.g., oxirane (epoxy),
oxetane, azetidine or aziridine groups). The invention includes the
homo- and copolymeric materials formed by the polymerization
reaction involving compounds of Formula I where R and R' contain at
least one polymerizable group.
[0043] A suitable reactive group may also be a hydroxy, amino,
carboxyl, isocyanato, dialkoxyalkylsilyl, or trialkoxysilyl group.
When the reactive group could interfere with reactions for
preparing the desired imide or methide, the reactive group can be
protected by reactants that are reversibly bound to it. For
example, a double bond may be protected as a dihalo derivative and
subsequently dehalogenated.
[0044] "Alkylene" refers to either straight or branched chain
divalent organic groups which may join at both ends to other groups
or atoms to form a ring. Preferred alkylene groups are ethylene and
propylene.
[0045] "Fluoroalkylene" refers to either straight or branched chain
divalent partially or fully fluorinated organic groups which may
join at both ends to other groups or atoms to form a ring.
Preferred fluoroalkylene groups are perfluoroethylene,
perfluoropropylene and perfluorobutylene.
[0046] Suitable cations, M.sup.m+, include alkali metal cations
(e.g., Li.sup.+, Na.sup.+, K.sup.+and Cs.sup.+), alkaline earth
metal cations (e.g., Mg.sup.2+, Ca.sup.2+, Sr.sup.2+and Ba.sup.2-),
Group IIIA cations (e.g., Al.sup.3+), transition metal cations
(e.g., Fe.sup.3+, Fe.sup.2+, Zn.sup.2+, Ti.sup.4+and Cu.sup.2+),
rare earth metal cations (e.g., Ce.sup.4+and La.sup.3+), ammonium
cations (i.e., R.sub.4N.sup.+, where R is independently alkyl,
preferably having from 1 to 4 carbon atoms, aryl or hydrogen),
sulfonium cations (i.e., R.sub.3S.sup.+), iodonium cations (i.e.,
R.sub.2I.sup.+), phosphonium cations (i.e., R.sub.4P.sup.+) and
protons (i.e., H.sup.+). Suitable cations also include
organometallic cations such as ferrocenium cation, cyclopentadienyl
(arene)M.sup.m+, (arene) M(CO).sub.3.sup.m+,
(arene).sub.2M.sup.m+and (cyclopentadienyl).sub.2
M(CH.sub.3).sup.m+, wherein M is a transition metal. Preferably,
for many battery applications, the cation is an alkali metal
cation; most preferably, the cation is a lithium cation.
[0047] Suitable monovalent R and R' hydrocarbon groups include
CH.sub.3-, C.sub.2H.sub.5-, (CH.sub.3).sub.2CH--,
(CH.sub.3).sub.3CCH.sub.2-, C.sub.8H.sub.17-, C.sub.6H.sub.5-,
C.sub.10H.sub.7-, H.sub.3CC.sub.6H.sub.4-, O.sub.2NC.sub.6H.sub.4-,
FC.sub.6H.sub.4-, NCC.sub.6H.sub.4-,
(CF.sub.3).sub.2C.sub.6H.sub.3-, CH.sub.2.dbd.CH.sub.2-,
CH.sub.2.dbd.CHCH.sub.2-, CH.sub.2.dbd.C(CH.sub.3- )--,
CH.sub.2.dbd.CHC(O)OC.sub.2H.sub.4-,
CH.sub.2.dbd.C(CH.sub.3)C(O)OC.s- ub.2H.sub.4-,
CH.sub.2.dbd.CH--C.sub.6H.sub.4-, HC.ident.CCH.sub.2-,
OCN(CH.sub.2).sub.6NH--, OCN--C.sub.6H.sub.4-, HOC.sub.2H.sub.4-,
HOCH.sub.2CH(OH)CH.sub.2-, H.sub.2NC.sub.2H.sub.4-,
(CH.sub.3O).sub.3SiC.sub.3H.sub.6-,
(CH.sub.3O).sub.2(CH.sub.3)SiC.sub.3H- .sub.6-, 2
[0048] Suitable divalent groups formed when two R groups, two R'
groups, or an R and R' group are taken together include
--CH.sub.2CH.sub.2-, -CH.sub.2CH(--CH.sub.3)--, 3
[0049] Suitable monovalent fluorocarbon groups include CF.sub.3-,
C.sub.2F.sub.5-, C.sub.4F.sub.9-, C.sub.8F.sub.17,
(CF.sub.3).sub.2NC.sub.2F.sub.4-, CF.sub.3OC.sub.2F.sub.4-. 4
[0050] Suitable divalent fluorocarbon groups formed when two R'
groups are taken together include --CF.sub.2CF.sub.2-, and
--CF.sub.2CF(CF.sub.3)--.
[0051] Examples of particularly suitable sulfonylimide anions
include the following: 5
[0052] In general, the sulfonylimide compounds of this invention
can be prepared by reacting the appropriate hydroxylic organic
precursor (e.g., alcohol or phenol) or aminic organic precursor
(e.g., amine or aniline) with a sulfonyl halide. The reaction is
typically run in an aprotic solvent (e.g., acetonitrile) with a
molar excess of tertiary amine (e.g., triethylamine) to consume the
hydrogen halide acid generated and thus drive the reaction to
completion. The reaction should be run at a temperature of
approximately 0.degree. C. to 25.degree. C. to keep the exotherm
under control. The resulting triethylammonium salt solution can be
filtered to remove any solid by-products, and the filtrate can be
stripped of solvent. To exchange the triethylammonium cation with
the desired cation, neutralization can be conducted with an aqueous
solution or dispersion of the base of the desired cation (e.g., its
hydroxide, oxide or carbonate), water is removed, and the resulting
solids washed with a water-immiscible solvent (e.g., diethyl
ether). Further purification is possible by re-dissolving the
solids in tetrahydrofuran and passing this solution through a short
column of alumina.
[0053] Sulfonylimides having oxygen or nitrogen heteroatoms
adjacent to the imide group may be conveniently prepared by
reacting imidobis(sulfuryl chloride) (IBSC, HN(SO.sub.2Cl).sub.2)
with either a hydroxylic or aminic organic precursor as described
by Argyropoulos et al. in Journal of Applied Chemistry, 26,
3073-3084 (1981), using the reaction conditions described
above.
[0054] Procedures for making perfluoroalkanesulfonyl-substituted
imide compounds are described in U.S. Pat. No. 5,652,072, which is
herein incorporated by reference.
[0055] For some battery electrolyte compositions, it is desirable
to add other conductive salts in order to maximize battery
performance. Typically any conventional conductive salt known for
chemical power sources may be used. For example, an additional
conductive compound may include:
[0056] a cation selected from the group consisting of an alkali
metal; an alkaline earth metal; a Group IIB metal; a Group IIIB
metal; a transition metal; a rare earth metal; an ammonium cation
such as tetraalkylammonium and trialkylammonium; and a proton;
and
[0057] an anion selected from the group consisting of
NO.sub.3.sup.-, Br.sup.-, I.sup.-, BF.sub.4.sup.-, PF.sub.6.sup.-,
AsF.sub.6.sup.-, ClO.sub.4.sup.-, SbF.sub.6.sup.- and a
perfluorinated anion, wherein the perfluorinated anion may be:
[0058] a perfluorinated sulfonate anion of the formula
R.sub.f0SO.sub.3.sup.-, in which R.sub.f0 is a perfluoroalkyl group
having between 1 and 12 carbon atoms which may contain straight,
branched or cyclic moieties;
[0059] a perfluorinated acyclic imide anion of the formula
(R.sub.f1SO.sub.2)(R.sub.f2SO.sub.2)N.sup.-, in which R.sub.f1 and
R.sub.f2 are each independently a perfluoroalkyl group of 1 to 8
carbon atoms which may contain straight, branched or cyclic
moieties, with R.sub.f1 and R.sub.f2 having a total of up to 12
carbon atoms;
[0060] a perfluorinated cyclic imide anion of the formula 6
[0061] in which R'.sub.f1 is a perfluoroalkylene moiety of 2 to 4
carbon atoms, optionally substituted by a straight or branched
perfluoroalkyl group of 1 to 2 carbon atoms, with R'.sub.f1 having
a total of up to 6 carbon atoms;
[0062] a perfluorinated sulfonate, imide or methide anion of the
formula (R.sub.f3)(R.sub.f4)N(CF.sub.2).sub.n,SO.sub.2X.sup.-) or
7
[0063] in which R.sub.f3 and Rf.sub.4 independently are
--C.sub.mF.sub.2m+1, or --(CF.sub.2).sub.qSO.sub.2X.sup.-, and
R'.sub.f2 and R'.sub.f3 independently are perfluoroalkylene
moieties having the formula --C.sub.rF.sub.2r-; wherein X.sup.-is
--O.sup.-, --N.sup.-SO.sub.2(R.sub.f5) or 8
[0064] wherein R.sub.f5, R.sub.f6 and R.sub.f7 independently are
--C.sub.mF.sub.2m+1, --(CF.sub.2).sub.4-SO.sub.2-X.sup.-), 9
[0065] wherein R.sub.f8 and R.sub.f9 are each independently a
straight, branched or cyclic perfluoroalkyl group of 1 to 8 carbon
atoms, with R.sub.f8 and R.sub.f9 having a total of up to 12 carbon
atoms;
[0066] Z is --CF.sub.2-, --O--, --N(R.sub.f10)-- or --SF.sub.4-,
wherein R.sub.f10 is --C.sub.mF.sub.2m+1, or
--(CF.sub.2).sub.q-SO.sub.2-X);
[0067] R'.sub.f4 and R'.sub.f5 independently are perfluoroalkylene
moieties having the formula --C.sub.rF.sub.2r-;
[0068] n' is 1 to 4 inclusive; m is 1 to 12 inclusive, preferably 1
to 8 inclusive; r is 1 to 4 inclusive; and q is 1 to 4
inclusive;
[0069] a bis(perfluoroalkylsulfonyl) methide anion of the formula
(R.sub.f11SO.sub.2)C.sup.-(R)(SO.sub.2R.sub.f.sub.12), in which
R.sub.f11 and R.sub.f.sub.12 independently are perfluoroalkyl
groups having between 1 and 12 carbon atoms, preferably between 1
and 4 carbon atoms, and R is H, Br, Cl, I, an alkyl group having
between 1 and 20 carbon atoms, an aryl group or an alkaryl
group;
[0070] and a tris(perfluoroalkylsulfonyl) methide anion of the
formula
.sup.-C(SO.sub.2R.sub.f13)(SO.sub.2R.sub.f14)(SO.sub.2R.sub.f15),
in which R.sub.f13, R.sub.f14, and R.sub.f15 independently are
perfluoroalkyl groups having between 1 and 12 carbon atoms,
preferably between 1 and 4 carbon atoms.
[0071] Preferred additional conductive salts includes those having
a lithium cation and having an anion selected from the group
consisting of PF.sub.6.sup.-anion; ClO.sub.4.sup.-anion;
BF.sub.4.sup.-anion; a perfluorinated sulfonate anion of the
formula R.sub.fSO.sub.3.sup.-, in which R.sub.f0 is a
perfluoroalkyl group having from 1 to 8 carbon atoms; a
perfluorinated acyclic imide anion of the formula
(R.sub.f1SO.sub.2)(R.sub.f2SO.sub.2)N.sup.-, wherein R.sub.f1 and
R.sub.f2 are each independently a straight or branched
perfluoroalkyl group having from 1 to 8 carbon atoms, with R.sub.f1
and R.sub.f2 having a total of up to 10 carbon atoms; a
perfluorinated cyclic imide anion of the formula: 10
[0072] in which R'.sub.f1 is a perfluoroalkylene moiety of 2 to 4
carbon atoms, optionally substituted by a straight or branched
perfluoroalkyl group of 1 to 2 carbon atoms, with R'.sub.f1 having
a total of up to 6 carbon atoms; and a tris(perfluoroalkylsulfonyl)
methide anion of the formula
.sup.-C(SO.sub.2R.sub.f13)(SO.sub.2R.sub.f14)(SO.sub.2R.sub.f15),
in which R.sub.f13, R.sub.f14, and R.sub.f15 independently are
perfluoroalkyl groups having between 1 and 4 carbon atoms.
[0073] Most preferred additional conductive salts include
LiBF.sub.4, LiAsF.sub.6, LiClO.sub.4, LiPF.sub.6, LiNO.sub.3,
C.sub.4F.sub.9SO.sub.3L- i, C.sub.8F.sub.17SO.sub.3Li,
(CF.sub.3SO.sub.2).sub.2NLi, (C.sub.2F.sub.5SO.sub.2).sub.2NLi,
(C.sub.8F.sub.17SO.sub.2)(CF.sub.3SO.s- ub.2)NLi,
(C.sub.8F.sub.17SO.sub.2)(C.sub.2F.sub.5SO.sub.2)NLi,
(CF.sub.3SO.sub.2).sub.2NNa, [(CF.sub.3SO.sub.2).sub.2N].sub.3A1,
(CF.sub.3).sub.2NC.sub.2F.sub.4SO.sub.3Li,
(CF.sub.3SO.sub.2).sub.3CLi,
C.sub.6H.sub.5SO.sub.2NLiSO.sub.2CF.sub.3,
((CF.sub.3).sub.2NC.sub.2F.sub- .4SO.sub.2).sub.2NLi and mixtures
thereof
[0074] To form the electrolyte composition, the conductive
compounds are mixed with the matrix material such that the salts
are at least partially dissolved or dispersed in the matrix
material. The salts are preferably employed at a concentration such
that the conductivity of the electrolyte solution is at or near its
maximum value, although a wide range of other concentrations will
also serve.
[0075] The matrix material may be in the form of a solid, liquid,
gel or a liquid impregnated porous membrane. For battery
applications, the matrix material is chosen to provide the
particular conductance, viscosity, mechanical strength, reactivity
and stability desired for the electrolyte.
[0076] Suitable matrix materials for preparing electrolyte
solutions can be liquid, polymeric or mixtures of polymer and
liquid. Examples of suitable solid matrix materials include
polymers and copolymers such as polyethers like poly(ethylene
oxide), polyesters, polyacrylates, polyphosphazenes, polysiloxanes,
poly(propylene oxide), fluoropolymers (e.g., poly(vinylidene
fluoride)), and poly(acrylonitrile), as well as the polymers and
copolymers described in Armand et al., U.S. Pat. No. 4,505,997,
incorporated herein by reference, and mixtures thereof. The
polymers may be used in cross-linked or uncross-linked form and
plasticized. Such materials are generally anhydrous, i.e., have a
water content less than about 100 ppm, preferably less than about
50 ppm.
[0077] In batteries comprising a highly reducing electrode (such as
lithium metal) and a liquid matrix material, the liquid is
preferably a nonaqueous, polar, aprotic, organic solvent. Such
liquids are generally anhydrous, i.e., have a water content less
than about 100 ppm, preferably less than about 50 ppm. Examples of
suitable aprotic liquids include linear ethers such as diethyl
ether, diethylene glycol dimethyl ether, and 1,2-dimethoxyethane;
cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran,
dioxane, dioxolane, and 4-methyldioxolane; esters such as methyl
formate, ethyl formate, methyl acetate, dimethyl carbonate, diethyl
carbonate, propylene carbonate, ethylene carbonate, and
butyrolactones (e.g. gamma butyrolactone); nitrites such as
acetonitrile and benzonitrile; nitro compounds such as nitromethane
or nitrobenzene; amides such as N,N-dimethylformamide,
N,N-diethylformamide, and N-methylpyrrolidinone; sulfoxides such as
dimethyl sulfoxide; sulfones such as dimethylsulfone;
tetramethylene sulfone, and other sulfolanes; oxazolidinones such
as N-methyl-2-oxazolidinone and mixtures thereof Maximum
conductivities of the electrolyte salts of this invention in
typical nonaqueous, polar, aprotic liquid media (e.g., propylene
carbonate) are generally in the range of 0.1-20 mS (milliSiemens)
at room temperature, preferably greater than 1 mS.
[0078] Mixtures of matrix materials can be employed and are
sometimes preferred in tailoring the matrix material's properties
to provide optimum performance. In general, the amount of matrix
material is selected such that the total salt concentration ranges
from about 0.1 M (moles per liter) to about 2.0 M, preferably about
1 M.
[0079] A preferred chemical power source of the present invention
relates to a battery that includes at least one cathode, at least
one anode, a separator and liquid electrolyte comprising conductive
compounds and aprotic solvents.
[0080] The electrodes (i.e., anode and cathode) of, for example, a
lithium battery generally consist of a metallic foil and particles
of active material blended with a conductive diluent such as carbon
black or graphite bound into a plastic material binder. Typical
binders include polytetrafluoroethylene, polyvinylidene fluoride,
ethylene-propylene-dien- e (EPDM) terpolymer, and emulsified
styrene-butadiene rubber (SBR), and the binder may be cross-linked.
The binder may also be, for example, a solid carbon matrix formed
from the thermal decomposition of an organic compound. The metallic
foil or composite electrode material is generally applied to an
expanded metal screen or metal foil (preferably aluminum, copper or
nickel) current collector using a variety of processes such as
coating, casting, pressing or extrusion.
[0081] Examples of suitable battery anodes include lithium metal,
lithium metal alloys, sodium metal, carbon-based materials such as
graphite, coke, carbon fiber, pitch, transition metal oxides (such
as LiTi.sub.5O.sub.12 and LiWO.sub.2), and lithiated tin oxide. In
the case of lithium ion batteries, the lithium may be intercalated
into a host material such as carbon (i.e., to give lithiated
carbon) or carbon alloyed with other elements (such as silicon,
boron and nitrogen), a conductive polymer, or an inorganic host
that is intercalatable (such as Li.sub.xTi.sub.5O.sub.12). The
material comprising the anode may be carried on foil (e.g., nickel
and copper) backing or pressed into expanded metal screen and
alloyed with various other metals.
[0082] Examples of suitable cathode materials include graphite,
amorphous carbon, Li.sub.xCoO.sub.2, Li.sub.xNiO.sub.2, Co-doped
Li.sub.xNiO.sub.2, Li.sub.xMn.sub.2O.sub.4, Li.sub.xMnO.sub.2,
V.sub.2O.sub.5, V.sub.6O.sub.13, LiV.sub.3O.sub.8,
Ba.sub.2SmNiO.sub.5, SmMnO.sub.3, Sm.sub.3Fe.sub.5O.sub.12,
EuFeO.sub.3, EuFe.sub.5O.sub.12, EuMnO.sub.3, LaNiO.sub.3,
La.sub.2CoO.sub.4 and LaMnO.sub.3 (including the charged and
discharged forms of these materials), and conducting polymers such
as polypyrrole, polysulfides and polyvinylferrocene. In primary
batteries, the cathode can be fluorinated carbon (e.g.,
(CF).sub.n), SO.sub.2Cl.sub.2, Ag.sub.2CrO.sub.4, sulfur,
polysulfide, and an O.sub.2 or SO.sub.2 electrode.
[0083] Lithium batteries and supercapacitors usually contain a
separator to prevent short-circuiting between the cathode and
anode. The separator usually consists of a single-ply or multi-ply
sheet of microporous polymer (typically polyolefin, e.g.,
polyethylene, polypropylene, or combinations thereof) having a
predetermined length and width and having a thickness of less than
10 mils (0.025 cm). For example, see U.S. Pat. Nos. 3,351,495
(Larsen et al.), 4,539,256 (Shipman et al.), 4,731,304 (Lundquist
et al.) and 5,565,281 (Yu et al.). The pore size in these
microporous membranes, typically about 5 microns in diameter, is
sufficiently large to allow transport of ions but is sufficiently
small to prevent cathode/anode contact, either directly or from
particle penetration or dendrites which can form on the
electrodes.
[0084] The novel compounds of this invention can also be employed
in non-electrolyte applications. For example, the salts of Formula
I are useful as surfactants when the hydrocarbon groups of R and/or
R' contain in the range of 8 to 18 carbon atoms or when the
fluoroalkyl group of R' contains in the range of 4 to 12 carbon
atoms. Examples of such useful surfactant salt anions include
C.sub.8F.sub.17SO.sub.2N.sup.-SO.sub.2OCH(- CH.sub.3).sub.2,
(C.sub.12H.sub.25OSO.sub.2).sub.2N.sup.-and
C.sub.8F.sub.17SO.sub.2N.sup.-SO.sub.2OC.sub.12H.sub.25; surfactant
salt cations can be those commonly used in anionic surfactants,
such as alkali metal, alkaline earth metal or ammonium. The salts
and acids are also potentially useful as catalysts, antistats and
as cationic photoinitiators; examples of such useful compounds are
C.sub.6H.sub.5OSO.sub.2NHSO.sub.2CF.sub.3,
(CH.sub.3).sub.4P.sup.+-N(SO.s- ub.2OC.sub.6H.sub.5).sub.2 and
(C.sub.6H.sub.5).sub.3S.sup.+-N(SO.sub.2CF.-
sub.3)(SO.sub.2OC.sub.6H.sub.5).
[0085] The invention is illustrated further by, but is not intended
to be limited to, the following examples.
EXAMPLES
[0086] Note: All electrolyte salt samples were stored and handled
in a nitrogen- or argon-filled dry box (Vacuum Atmospheres Inc.) to
prevent contamination by water.
[0087] TEST METHODS
[0088] Conductivity
[0089] Conductivity measurements for liquid electrolytes were
generally made using a 1 molar (1 M) electrolyte derived from
carefully purified and dried components. The 1 M electrolyte was
made by dissolving 10 millimoles of electrolytic compound in 10 mL
of a 50/50 (vol) mixture of propylene carbonate
(PC)/1,2-dimethoxyethane (DME) or ethylene carbonate (EC)/dimethyl
carbonate (DMC). 10 mL of the resulting electrolyte was placed in a
glass container with a conductivity cell having K=1.0/cm (Model No.
3403, available from YSI Inc., Yellow Spring, Ohio), all kept in a
dry box before use. During all times, water contamination in the
electrolyte was kept below 30 ppm, as determined by Karl Fischer
titration. Impedance response was then measured in milli-Siemens
per square centimeter (mS/cm) using a PAR Model 273
potentiostat/galvanometer (available from EG&G Princeton
Applied Research, Princeton, N.J.), equipped with a frequency
response analyzer (Model 1260, available from Schlumberger,
Billerica, Mass.). The impedance response for each cell was
measured using an AC signal of 5-10 mv over a frequency response of
100,000 to 1 Hz, using Model 398 Electrochemical Software
(available from EG&G Princeton Applied Research). The
conductivity was then calculated from the impedance response.
[0090] Other concentrations, ranging from 0.2-2.0 M, were also
evaluated to identify the concentration for maximum
conductivity.
[0091] SOURCES, PREPARATIONS FOR CONDUCTIVE SALTS
[0092] Salt 1
[0093] 17 g of catechol (1,2-dihydroxybenzene, available from
Aldrich Chemical Co., Milwaukee, Wis.) was dissolved in 75 g of
anhydrous acetonitrile. To this was added 42 g of imidobis(sulfuryl
chloride) (prepared as described in "Inorganic Synthesis," Vol.
VIII, 1966, p. 105) in 90 g of anhydrous acetonitrile. The
resulting solution was cooled to 0.degree. C., 85 g of anhydrous
triethylamine was added dropwise, and the mixture was allowed to
react by stirring for 1 hour at 0.degree. C., followed by 1 hour at
room temperature. The reaction mixture was filtered and the solvent
was removed in vacu to give a brown-red oil. The resulting oil was
neutralized with 660.6 g of aqueous 1 M LiOH (99.995% pure,
available from Aldrich Chem. Co.). The water was removed and the
resulting solids were washed twice with 250 mL aliquots of diethyl
ether. The ether was removed to give 32.6 g of a white solid, which
was further purified by re-dissolving in tetrahydrofuran and
passing the resulting solution through a short column of basic
alumina. The recovered compound was identified as being 11
[0094] NMR analysis (CD.sub.3CN): .sup.1H, 7.27 ppm (m, 2 H) 7.33
ppm (m, 2 H), .sup.13C, 118, 124, 128 ppm. Chloride ion content: 12
ppm as measured by argentometric titration using silver nitrate
titrant. Elemental analysis: 28.33% C, 1.69% H, 5.28% N, 24.37% S,
2.59% Li, 37.74% O(theo. 28.02% C, 1.57% H, 5.45% N, 24.93% S,
2.70% Li and 37.33% O).
[0095] Salt 2
[0096] Salt 2, [(CH.sub.3).sub.2CHOSO.sub.2].sub.2NLi, was prepared
using essentially the same procedure as described for Salt 1,
except that isopropyl alcohol was reacted with imidobis(sulfuryl
chloride) in the presence of excess triethylamine. NMR (D.sub.2O):
.sup.1H, 1.33 ppm (d, 12 H, J=6.5 Hz) 4.65 ppm (septet, 2 H,
J=6.5).
[0097] Salt 3
[0098] Salt 3, [(CH.sub.3).sub.2NSO.sub.2](CF.sub.3SO.sub.2)NLi,
was prepared using essentially the same procedure as described for
Salt 1, except that trifluoromethylsulfonamide was reacted with
dimethylsulfamoyl chloride in the presence of excess triethylamine.
NMR (CD.sub.3CN): .sup.1H, 2.62 ppm (s), .sup.19F -77.9 ppm
(s).
[0099] Salt 4
[0100] Salt 4, 12
[0101] was prepared using essentially the same procedure as
described for Salt 1, except that 8.6 g of 2,2'-dihydroxybiphenyl
was reacted with 10.0 g of imidobis(sulfuryl chloride) in the
presence of excess triethylamine, providing a 39% yield of the
title product. .sup.1HNMR (CD.sub.3CN): .delta.=7.23 dd, 7.34 dt,
7.46 dt, 7.54 dd ppm. 13CNMR (CD.sub.3CN): .delta.=123.7, 127.3,
130.5, 131.0, 131.9, 150.7 ppm MS negative ion laser desorption:
M.sup.-: m/z=326; [M.sup.---SO.sub.3]: m/z=246; [M.sup.-2SO.sub.3]:
m/z=166.
[0102] Salt 5
[0103] Salt 5,
(C.sub.6H.sub.5)SO.sub.2NLiSO.sub.2N(CH.sub.3).sub.2, was prepared
using essentially the same procedure as described for Salt 1,
except that benzenesulfonamide was reacted with dimethylsulfamoyl
chloride in the presence of excess triethylamine.
[0104] The measured conductivities for Salts 1-5 are presented in
Table 1.
1TABLE 1 Compound Solvent Conductivity, Ex. Evaluated Blend MS/cm
(molarity) 1 Salt 1 EC/DMC 7.2 (0.8 M) 2 Salt 2 EC/DMC 2.0 (0.2 M)*
3 Salt 3 EC/DMC 4.4 (0.6 M) 4 Salt 4 EC/DMC 1.2 (1 M) 5 Salt 5
EC/DMC 0.83 (0.2 M)* *Salt solubility was low
[0105] The data in Table 1 show that all of the salts exhibited
fair to good conductivity in the solvent blend. This is surprising,
considering that the salts have little or no organofluorine in
their structures. Salt 1, the fluorine-free catechol derivative,
imparted especially high conductivity to the electrolyte.
* * * * *