U.S. patent application number 10/489385 was filed with the patent office on 2005-03-10 for proton-conducting membrane and the use of the same.
Invention is credited to Calundann, Gordon, Kiefer, Joachim, Sansone, Michael J, Uensal, Oemer.
Application Number | 20050053820 10/489385 |
Document ID | / |
Family ID | 7698702 |
Filed Date | 2005-03-10 |
United States Patent
Application |
20050053820 |
Kind Code |
A1 |
Calundann, Gordon ; et
al. |
March 10, 2005 |
Proton-conducting membrane and the use of the same
Abstract
The present invention relates to a novel proton-conducting
polymer membrane based on polyazoles which can, because of its
excellent chemical and thermal properties, be used in a variety of
ways and is particularly useful as polymer electrolyte membrane
(PEM) to produce membrane electrode units for PEM fuel cells.
Inventors: |
Calundann, Gordon; (North
Plainfield, NJ) ; Sansone, Michael J; (Berkeley
Heights, NJ) ; Uensal, Oemer; (Mainz, DE) ;
Kiefer, Joachim; (Losheim am See, DE) |
Correspondence
Address: |
HAMILTON, BROOK, SMITH & REYNOLDS, P.C.
530 VIRGINIA ROAD
P.O. BOX 9133
CONCORD
MA
01742-9133
US
|
Family ID: |
7698702 |
Appl. No.: |
10/489385 |
Filed: |
October 21, 2004 |
PCT Filed: |
August 29, 2002 |
PCT NO: |
PCT/EP02/09629 |
Current U.S.
Class: |
429/413 ;
429/450; 429/483; 429/492; 429/516; 521/27 |
Current CPC
Class: |
Y02E 60/50 20130101;
B01D 71/62 20130101; B01D 2323/26 20130101; H01M 8/1081 20130101;
B01D 67/0011 20130101; C08J 5/2256 20130101; H01M 8/1048 20130101;
H01M 8/1088 20130101; H01M 8/103 20130101; H01M 8/1032 20130101;
Y02P 70/50 20151101; B01D 2323/08 20130101; H01M 8/1027 20130101;
C08J 2379/06 20130101; H01M 8/0293 20130101 |
Class at
Publication: |
429/033 ;
521/027; 429/030 |
International
Class: |
H01M 008/10; C08J
005/22 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 12, 2001 |
DE |
101 44 815.5 |
Claims
1-22. (cancelled).
23. A proton-conducting polymer membrane based on polyazoles which
has a concentration of phosphoric acid expressed as mol of acid per
mol of recurring unit of the polymer of from 12 to 20 and is
obtainable by a process comprising the steps A) dissolving a
polyazole polymer in polyphosphoric acid to form a solution, B)
heating the solution obtainable as described in step A) to
temperatures of up to 400.degree. c, under inert gas, C)
formulating a membrane on a support using the solution of the
polyazole polymer from step B), and D) treating the membrane formed
in step C) in the presence of moisture at temperatures and for a
time which are sufficient for the membrane to become
self-supporting so that it can be detached from the support without
damage.
24. A membrane as claimed in claim 23, characterized in that the
polyphosphoric acid used in step A) has an assay calculated as
P.sub.2O.sub.5 (acidimetric) of at least 85%.
25. A membrane as claimed in claim 23, characterized in that a
dispersion/suspension instead of a solution of the polymer is
produced in step A).
26. A membrane as claimed in claim 23, characterized in that the
polymer used in step A) comprises recurring azole units of the
formula (I) and/or (II) 4where Ar are identical or different and
are each a tetravalent aromatic or heteroaromatic group which may
have one or more rings, Ar.sup.1 are identical or different and are
each a divalent aromatic or heteroaromatic group which may have one
or more rings, Ar.sup.2 are identical or different and are each a
divalent or trivalent aromatic or heteroaromatic group which may
have one or more rings, X are identical or different and are each
oxygen, sulfur or an amino group bearing a hydrogen atom, a group
having 1-20 carbon atoms, a branched or unbranched alkyl or alkoxy
group, and an aryl group as further radical.
27. A membrane as claimed in claim 26, wherein X are identical or
different and a branched or unbranched alkyl or alkoxy group.
28. A membrane as claimed in claim 23, characterized in that a
polymer selected from the group consisting of polybenzimidazole,
poly(pyridines), poly(pyrimidines), polyimidazoles,
polybenzothiazoles, polybenzoxazoles, polyoxadiazoles,
polyquinoxalines, polythiadiazoles and poly(tetrazapyrenes) is used
in step A).
29. A membrane as claimed in claim 23, characterized in that the
polymer used in step A) comprises one or more recurring
benzimidazole units of the formula 56where n and m are each an
integer greater than or equal to 10.
30. A membrane as claimed in claim 29, where n and m are each an
integer greater than or equal to 100.
31. A membrane as claimed in claim 23, characterized in that the
viscosity is adjusted by addition of phosphoric acid after step B)
and before step C).
32. A membrane as claimed in claim 23, characterized in that the
membrane produced in step C) is treated in the presence of moisture
at temperatures and for a time until the membrane is
self-supporting and can be detached from the support without
damage.
33. A membrane as claimed in claim 23, characterized in that the
treatment of the membrane in step D) is carried out at temperatures
of from >0.degree. C. to 150.degree. C. in the presence of
moisture or water, dilute phosphoric acid and/or water vapor.
34. A membrane as claimed in claim 33, characterized in that the
treatment of the membrane in step D) is carried out at temperatures
of from 10.degree. C. to 120.degree. C.
35. A membrane as claimed in claim 34, characterized in that the
treatment of the membrane in step D) is carried out at temperatures
of from room temperature (20.degree. C.) to 90.degree. C.
36. A membrane as claimed in claim 23, characterized in that the
treatment of the membrane in step D) is carried out for from 10
second to 300 hours.
37. A membrane of claim 36, characterized in that the treatment of
the membrane in step D) is carried out for from 1 minute to 200
hours.
38. A membrane as claimed in claim 23, characterized in that
subsequent to the treatment in step D) the membrane is crosslinked
by action of IR or NIR.
39. A membrane as claimed in claim 23, characterized in that an
electrode is chosen as the support in step C).
40. A membrane as claimed in claim 23, characterized in that the
membrane formed in step C) has a thickness of from 20 to 2000
.mu.m.
41. A membrane as claimed in claim 40, characterized in that the
membrane formed in step C) has a thickness of from 30 to 1500
.mu.m.
42. A membrane as claimed in claim 41, characterized in that the
membrane formed in step C) has a thickness of from 50 to 1200
.mu.m.
43. A membrane as claimed in claim 23, characterized in that the
membrane formed in step D) has a thickness of from 15 to 400 .mu.m
and is self-supporting.
44. A membrane as claimed in claim 43, characterized in that the
membrane formed in step D) has a thickness of from 20 to 200
.mu.m.
45. A membrane as claimed in claim 44, characterized in that the
membrane formed in step D) has a thickness of from 20 to 150
.mu.m.
46. A membrane as claimed in claim 23, characterized in that it has
a layer comprising a catalytically active component.
47. An electrode provided with a proton-conducting polymer coating
based on polyazoles which has a concentration of phosphoric acid
expressed as mol of acid per mol of recurring unit of the polymer
of from 12 to 20 which membrane is obtainable by a process
comprising the steps A) dissolving a polyazole polymer in
polyphosphoric acid to form a solution, B) heating the solution
obtainable as described in step A) to temperatures of up to
400.degree. C., under inert gas, C) applying a layer to an
electrode using the solution of the polyazole polymer from step B),
and D) treating the layer formed in step C) at temperatures of from
0.degree. C. to 150.degree. C. in the presence of moisture.
48. An electrode as claimed in claim 47, characterized in that the
coating has a thickness of from 2 to 300 .mu.m.
49. An electrode as claimed in claim 48, characterized in that the
coating has a thickness of from 5 to 250 .mu.m.
50. An electrode as claimed in claim 49, characterized in that the
coating has a thickness of from 10 to 100 .mu.m.
51. A membrane-electrode unit comprising: at least one electrode
provided with a proton-conducting polymer coating based on
polyazoles which has a concentration of phosphoric acid expressed
as mol of acid per mol of recurring unit of the polymer of from 12
to 20 which membrane is obtainable by a process comprising the
steps i) dissolving a polyazole polymer in polyphosphoric acid to
form a solution, ii) heating the solution obtainable as described
in step i) to temperatures of up to 400.degree. C., under inert
gas, iii) applying a layer to an electrode using the solution of
the polyazole polymer from step ii), and iv) treating the layer
formed in step iii) at temperatures of from 0.degree. C. to
150.degree. C. in the presence of moisture; and at least one
proton-conducting polymer membrane based on polyazoles which has a
concentration of phosphoric acid expressed as mol of acid per mol
of recurring unit of the polymer of from 12 to 20 and is obtainable
by a process comprising the steps A) dissolving a polyazole polymer
in polyphosphoric acid to form a solution, B) heating the solution
obtainable as described in step A) to temperatures of up to
400.degree. C., under inert gas, C) formulating a membrane on a
support using the solution of the polyazole polymer from step B),
and D) treating of the membrane formed in step C) in the presence
of moisture at temperatures and for a time which are sufficient for
the membrane to become self-supporting so that it can be detached
from the support without damage.
52. A membrane-electrode unit comprising: at least one electrode,
and at least one proton-conducting polymer membrane based on
polyazoles which has a concentration of phosphoric acid expressed
as mol of acid per mol of recurring unit of the polymer of from 12
to 20 and is obtainable by a process comprising the steps A)
dissolving a polyazole polymer in polyphosphoric acid to form a
solution, B) heating the solution obtainable as described in step
A) to temperatures of up to 400.degree. C., under inert gas, C)
formulating a membrane on a support using the solution of the
polyazole polymer from step B), and D) treating of the membrane
formed in step C) in the presence of moisture at temperatures and
for a time which are sufficient for the membrane to become
self-supporting so that it can be detached from the support without
damage.
53. A membrane-electrode unit as claimed in claim 52, characterized
in that the polyphosphoric acid used in step A) has an assay
calculated as P.sub.2O.sub.5 (acidimetric) of at least 85%.
54. A membrane-electrode unit as claimed in claim 52, characterized
in that a dispersion/suspension instead of a solution of the
polymer is produced in step A).
55. A membrane as claimed in claim 52, characterized in that the
polymer used in step A) comprises recurring azole units of the
formula (I) and/or (II) 7where Ar are identical or different and
are each a tetravalent aromatic or heteroaromatic group which may
have one or more rings, Ar.sup.1 are identical or different and are
each a divalent aromatic or heteroaromatic group which may have one
or more rings, Ar.sup.2 are identical or different and are each a
divalent or trivalent aromatic or heteroaromatic group which may
have one or more rings, X are identical or different and are each
oxygen, sulfur or an amino group bearing a hydrogen atom, a group
having 1-20 carbon atoms, a branched or unbranched alkyl or alkoxy
group, and an aryl group as further radical.
56. A membrane-electrode unit as claimed in claim 55, wherein X are
identical or different and a branched or unbranched alkyl or alkoxy
group.
57. A membrane-electrode unit as claimed in claim 52, characterized
in that a polymer selected from the group consisting of
polybenzimidazole, poly(pyridines), poly(pyrimidines),
polyimidazoles, polybenzothiazoles, polybenzoxazoles,
polyoxadiazoles, polyquinoxalines, polythiadiazoles and
poly(tetrazapyrenes) is used in step A).
58. A membrane-electrode unit as claimed in claim 52, characterized
in that the polymer used in step A) comprises one or more recurring
benzimidazole units of the formula 89where n and m are each an
integer greater than or equal to 10.
59. A membrane-electrode unit as claimed in claim 58, where n and m
are each an integer greater than or equal to 100.
60. A membrane-electrode unit as claimed in claim 52, characterized
in that the viscosity is adjusted by addition of phosphoric acid
after step B) and before step C).
61. A membrane-electrode unit as claimed in claim 52, characterized
in that the membrane produced in step C) is treated in the presence
of moisture at temperatures and for a time until the membrane is
self-supporting and can be detached from the support without
damage.
62. A membrane-electrode unit as claimed in claim 52, characterized
in that the treatment of the membrane in step D) is carried out at
temperatures of from >0.degree. C. to 150.degree. C. in the
presence of moisture or water, dilute phosphoric acid and/or water
vapor.
63. A membrane-electrode unit as claimed in claim 62, characterized
in that the treatment of the membrane in step D) is carried out at
temperatures of from 10.degree. C. to 120.degree. C.
64. A membrane-electrode unit as claimed in claim 63, characterized
in that the treatment of the membrane in step D) is carried out at
temperatures of from room temperature (20.degree. C.) to 90.degree.
C.
65. A membrane-electrode unit as claimed in claim 52, characterized
in that the treatment of the membrane in step D) is carried out for
from 10 second to 300 hours.
66. A membrane-electrode unit as claimed in claim 65, characterized
in that the treatment of the membrane in step D) is carried out for
from 1 minute to 200 hours.
67. A membrane-electrode unit as claimed in claim 52, characterized
in that subsequent to the treatment in step D) the membrane is
crosslinked by action of IR or NIR.
68. A membrane-electrode unit as claimed in claim 52, characterized
in that an electrode is chosen as the support in step C).
69. A membrane-electrode unit as claimed in claim 52, characterized
in that the membrane formed in step C) has a thickness of from 20
to 2000 .mu.m.
70. A membrane-electrode unit as claimed in claim 69, characterized
in that the membrane formed in step C) has a thickness of from 30
to 1500 .mu.m.
71. A membrane-electrode unit as claimed in claim 70, characterized
in that the membrane formed in step C) has a thickness of from 50
to 1200 .mu.m.
72. A membrane-electrode unit as claimed in claim 52, characterized
in that the membrane formed in step D) has a thickness of from 15
to 400 .mu.m and is self-supporting.
73. A membrane-electrode unit as claimed in claim 72, characterized
in that the membrane formed in step D) has a thickness of from 20
to 200 .mu.m.
74. A membrane-electrode unit as claimed in claim 73, characterized
in that the membrane formed in step D) has a thickness of from 20
to 150 .mu.m.
75. A membrane-electrode unit as claimed in claim 52, characterized
in that the membrane has a layer comprising a catalytically active
component.
76. A membrane-electrode unit as claimed in claim 52, characterized
in that the unit comprises at least one further polymer membrane
based on polyazoles and/or a polymer blend membrane comprising at
least one polymer based on polyazoles.
77. A fuel cell comprising one or more membrane-electrode units,
wherein the unit includes: at least one electrode, and at least one
proton-conducting polymer membrane based on polyazoles which has a
concentration of phosphoric acid expressed as mol of acid per mol
of recurring unit of the polymer of from 12 to 20 and is obtainable
by a process comprising the steps A) dissolving a polyazole polymer
in polyphosphoric acid to form a solution, B) heating the solution
obtainable as described in step A) to temperatures of up to
400.degree. C., under inert gas, C) formulating a membrane on a
support using the solution of the polyazole polymer from step B),
and D) treating the membrane formed in step C) in the presence of
moisture at temperatures and for a time which are sufficient for
the membrane to become self-supporting so that it can be detached
from the support without damage.
Description
[0001] The present invention relates to a novel proton-conducting
polymer membrane based on polyazoles which can, because of its
excellent chemical and thermal properties, be used in a variety of
ways and is particularly useful as polymer electrolyte membrane
(PEM) in PEM fuel cells.
[0002] Polyazoles such as polybenzimidazoles (.RTM.Celazole) have
been known for a long time. The preparation of such
polybenzimidazoles (PBI) is usually carried out by reacting
3,3',4,4'-tetraaminobiphenyl with isophthalic acid or
diphenylisophthalic acid or their esters in a solid-phase
polymerization. The prepolymer formed solidifies in the reactor and
is subsequently comminuted mechanically. The pulverulent prepolymer
is subsequently fully polymerized at temperatures of up to
400.degree. C. to give the desired polybenzimidazoles.
[0003] To produce polymer films, the PBI is dissolved in polar,
aprotic solvents such as dimethylacetamide (DMAc) and a film is
produced by classical methods.
[0004] Proton-conducting, i.e. acid-doped, polyazole membranes for
use in PEM fuel cells are already known. The basic polyazole films
are doped with concentrated phosphoric acid or sulfuric acid and
then act as proton conductors and separators in polymer electrolyte
membrane fuel cells (PEM fuel cells).
[0005] Due to the excellent properties of the polyazole polymer,
such polymer electrolyte membranes can, when converted into
membrane-electrode units (MEEs), be used in fuel cells at
continuous operating temperatures above 100.degree. C., in
particular above 120.degree. C. This high continuous operating
temperature allows the activity of the catalysts based on noble
metals present in the membrane-electrode unit (MEE) to be
increased. Particularly when using reforming products from
hydrocarbons, significant amounts of carbon monoxide are present in
the reformer gas and these usually have to be removed by means of a
complicated gas work-up or gas purification. The ability to
increase the operating temperature makes it possible to tolerate
significantly higher concentrations of CO impurities in long-term
operation.
[0006] The use of polymer electrolyte membranes based on polyazole
polymers enables, firstly, the complicated gas work-up or gas
purification to be omitted, at least in part, and, secondly, allows
the catalyst loading in the membrane-electrode unit to be reduced.
Both are indispensable prerequisites for wide use of PEM fuel cells
since otherwise the costs of a PEM fuel cell system are too
high.
[0007] The previously known acid-doped polymer membranes based on
polyazoles display an advantageous property profile. However, an
overall improvement in these properties has to be achieved in order
to be able to use PEM fuel cells in the intended applications, in
particular in the automobile sector and in decentralized power and
heat generation (stationary applications). In addition, the polymer
membranes known hitherto have a high content of dimethylacetamide
(DMAc) which cannot be removed completely by means of known drying
methods. The German patent application No. 10109829.4 describes a
polymer membrane based on polyazoles in the case of which the DMAc
contamination was eliminated. Although such polymer membranes
display improved mechanical properties, the specific conductivity
does not exceed 0.1 S/cm (at 120.degree. C.).
[0008] It is an object of the present invention to provide
acid-doped polymer membranes based on polyazoles which, firstly,
have the use advantages of the polymer membrane based on polyazoles
and, secondly, display an increased specific conductivity, in
particular at operating temperatures above 100.degree. C., and
additionally make do without humidification of the fuel gas.
[0009] We have now found that a proton-conducting membrane based on
polyazoles can be obtained when the commercially available
polyazole polymer is dissolved in polyphosphoric acid to produce
the membrane.
[0010] In the case of this novel membrane, the specific
after-treatment described in the German patent application No.
10109829.4 can be dispensed with. The doped polymer membranes
display a significantly improved proton conductivity and the
subsequent doping of the film is dispensed with.
[0011] The present invention provides a proton-conducting polymer
membrane based on polyazoles which is obtainable by a process
comprising the steps
[0012] A) Dissolution of the polyazole polymer in polyphosphoric
acid,
[0013] B) Heating of the solution obtainable as described in step
A) to temperatures of up to 400.degree. C., preferably up to
350.degree. C., in particular up to 300.degree. C., under inert
gas,
[0014] C) Formulation of a membrane on a support using the solution
of the polyazole polymer from step B), and
[0015] D) Treatment of the membrane formed in step C) until it is
self-supporting.
[0016] The polymers used in step A) comprise recurring azole units
of the formula (I) and/or (II) 1
[0017] where
[0018] Ar are identical or different and are eacha tetravalent
aromatic or heteroaromatic group which may have one or more
rings,
[0019] Ar.sup.1 are identical or different and are each a divalent
aromatic or heteroaromatic group which may have one or more
rings,
[0020] Ar.sup.2 are identical or different and are each a divalent
or trivalent aromatic or heteroaromatic group which may have one or
more rings,
[0021] X are identical or different and are each oxygen, sulfur or
an amino group bearing a hydrogen atom, a group having 1-20 carbon
atoms, preferably a branched or unbranched alkyl or alkoxy group,
or an aryl group as further radical.
[0022] Preferred aromatic or heteroaromatic groups are derived from
benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane,
diphenyldimethylmethane, bisphenone, diphenyl sulfone, quinoline,
pyridine, bipyridine, anthracene and phenanthrene, which may also
be substituted.
[0023] Ar.sup.1 can have any substitution pattern; in the case of
phenylene for example, Ar.sup.1 can be ortho-, meta- or
para-phenylene. Particularly preferred groups are derived from
benzene and biphenyls, which may also be substituted.
[0024] Preferred alkyl groups are short-chain alkyl groups having
from 1 to 4 carbon atoms, e.g. methyl, ethyl, n-propyl or i-propyl
and t-butyl groups.
[0025] Preferred aromatic groups are phenyl or naphthyl groups. The
alkyl groups and the aromatic groups may be substituted.
[0026] Preferred substituents are halogen atoms such as fluorine,
amino groups or short-chain alkyl groups such as methyl or ethyl
groups.
[0027] Preference is given to polyazoles comprising recurring units
of the formula (I) in which the radicals X are identical within a
recurring unit.
[0028] The polyazoles can in principle also comprise different
recurring units which differ, for example, in their radical X.
However, they preferably have only identical radicals X in a
recurring unit.
[0029] In a further embodiment of the present invention, the
polymer comprising recurring azole units is a copolymer comprising
at least two units of the formula (I) and/or (II) which differ from
one another. The polymers can be present as block copolymers
(diblock, triblock), random copolymers, periodic copolymers and/or
alternating polymers.
[0030] In a particularly preferred embodiment of the present
invention, the polymer comprising recurring azole units is a
polyazole which contains only units of the formula (I) and/or
(II).
[0031] The number of recurring azole units in the polymer is
preferably greater than or equal to 10. Particularly preferred
polymers have at least 100 recurring azole units.
[0032] For the purposes of the present invention, polymers
comprising recurring benzimidazole units are preferred. Some
examples of the extremely advantageous polymers comprising one or
more recurring benzimidazole units have the following formulae:
23
[0033] where n and m are each an integer greater than or equal to
10, preferably greater than or equal to 100.
[0034] The polyazoles used, but in particular the
polybenzimidazoles, have a high molecular weight. Measured as the
intrinsic viscosity, this is at least 0.2 dl/g, preferably from 0.2
to 3 dl/g.
[0035] Further preferred polyazole polymers are polyimidazoles,
polybenzothiazoles, polybenzoxazoles, polyoxadiazoles,
polyquinoxalines, polythiadiazoles, poly(pyridines),
poly(pyrimidines) and poly(tetrazapyrenes).
[0036] The polyphosphoric acid used in step A) is commercially
available polyphosphoric acid as can be obtained, for example, from
Riedel-de-Haen. The polyphosphoric acids
H.sub.n+2P.sub.nO.sub.3n+1(n>1) usually have an assay calculated
as P.sub.2O.sub.5 (acidimetric) of at least 83%. In place of a
solution of the prepolymer, a dispersion/suspension can also be
produced.
[0037] The mixture produced in step A) has a weight ratio of
polyphosphoric acid to polyazole polymer of from -1:10 000 to 10
000:1, preferably from 1:1 000 to 1 000:1, in particular from 1:100
to 100:1.
[0038] The formation of the polymer membrane in step C) is carried
out by means of measures (casting, spraying, doctor blade coating,
extrusion) which are known per se from the prior art for polymer
film production. As supports, it is possible to use all supports
which are inert under the conditions employed. To adjust the
viscosity, the solution can, if necessary, be admixed with dilute
or concentrated phosphoric acid (concentrated phosphoric acid, 85%)
and/or water. In this way, the viscosity can be set to the desired
value and the formation of the membrane can be made easier. The
thickness is from 20 to 2000 .mu.m, preferably from 30 to 1500
.mu.m, in particular from 50 to 1200 .mu.m.
[0039] The temperature of the heated solution is up to 400.degree.
C., preferably from 150 to 350.degree. C., in particular from 190
to 300.degree. C.
[0040] The membrane produced in step C) is treated at elevated
temperatures in the presence of moisture for a sufficient time
until the membrane is self-supporting, so that it can be detached
from the support without damage (step D).
[0041] The treatment of the membrane in step D) is carried out at
temperatures above 0.degree. C. and less than 150.degree. C.,
preferably at temperatures of from 10.degree. C. to 120.degree. C.,
in particular from room temperature (20.degree. C.) to 90.degree.
C., in the presence of moisture or water, dilute phosphoric acid
and/or water vapor. The treatment is preferably carried out at
atmospheric pressure, but can also be carried out at
superatmospheric pressure. It is important for the treatment to
occur in the presence of sufficient moisture so that the
polyphosphoric acid present contributes to strengthening of the
membrane as a result of partial hydrolysis to form low molecular
weight polyphosphoric acid and/or phosphoric acid.
[0042] The partial hydrolysis of the polyphosphoric acid in step D)
leads to strengthening of the membrane and to a decrease in the
thickness and formation of a membrane having a thickness of from 15
to 400 .mu.m, preferably from 20 to 200 .mu.m, in particular from
20 to 150 .mu.m, which is self-supporting.
[0043] The intramolecular and intermolecular structures (e.g.
networks of the polyazole with the polyphosphoric acid) present in
the polyphosphoric acid lead to ordered membrane formation which is
responsible for the particular properties of the membrane
formed.
[0044] The upper temperature limit for the treatment in step D) is
generally 150.degree. C. If moisture is present for an extremely
short time, for example in the case of superheated steam, this
steam can also be hotter than 150.degree. C. The important factor
in determining the upper temperature limit is the duration of the
treatment.
[0045] The partial hydrolysis (step D) can also be carried out in
temperature- and humidity-controlled chambers so that the
hydrolysis can be controlled in a targeted manner in the presence
of a defined amount of moisture. The amount of moisture can in this
case be set in a targeted manner by means of the temperature or
saturation of the environment in phosphoric contact with the
membrane, for example gases such as air, nitrogen, carbon dioxide
or other suitable gases, steam and/or dilute acid. The treatment
time is dependent on the above parameters chosen.
[0046] Furthermore, the treatment time is dependent on the
thickness of the membrane.
[0047] The treatment time is generally in the range from a few
seconds to some minutes, for example under the action of
superheated steam, or up to a number of days, for example in air at
room temperature and a low relative atmospheric humidity. The
treatment time is preferably from 10 seconds to 300 hours, in
particular from 1 minute to 200 hours.
[0048] If the partial hydrolysis is carried out at room temperature
(20.degree. C.) using ambient air having a relative atmospheric
humidity of 40-80%, the treatment time is from 1 to 200 hours.
[0049] The membrane obtained in step D) is self-supporting, i.e. it
can be detached from the support without damage and subsequently be
processed further immediately if desired.
[0050] The concentration of phosphoric acid and thus the
conductivity of the polymer membrane according to the invention can
be set via the degree of hydrolysis, i.e. the time, temperature and
ambient moisture level. According to the invention, the
concentration of phosphoric acid is reported as mole of acid per
mole of repeating units of the polymer. For the purposes of the
present invention, a concentration (mole of phosphoric acid per
repeating unit of the formula (III), i.e. polybenzimidazole) of
from 10 to 35, in particular from 12 to 20, is preferred. Such high
degrees of doping (concentrations) are very difficult or impossible
to achieve by doping polyazoles with commercially available
ortho-phosphoric acid and lead to the loss of mechanical
integrity.
[0051] Subsequent to the treatment as described in step D), the
membrane can be crosslinked on the surface by action of heat in the
presence of atmospheric oxygen. This hardening of the membrane
surface effects an additional improvement in the properties of the
membrane.
[0052] Crosslinking can also be achieved by action of IR or NIR
(IR=infrared, i.e. light having a wavelength of more than 700 nm;
NIR=near IR, i.e. light having a wavelength in the range from about
700 to 2000 nm or an energy in the range from about 0.6 to 1.75
eV). A further method is irradiation with .beta.-rays. The
radiation dose is in this case in the range from 5 to 200 kGy.
[0053] The polymer membrane of the invention has improved materials
properties compared to the doped polymer membranes known hitherto.
In particular, it displays improved performance compared to known
doped polymer membranes. This is due, in particular, to an improved
proton conductivity.
[0054] This is at least 0.1 S/cm, preferably at least 0.12 S/cm, at
a temperature of 120.degree. C.
[0055] To achieve a further improvement in the use properties,
fillers, in particular proton-conducting fillers, and also
additional acids can be additionally added to the membrane. The
addition can be carried out either during step A or B.
[0056] Nonlimiting examples of proton-conducting fillers are
[0057] Sulfates such as CsHSO.sub.4, Fe(SO.sub.4).sub.2,
(NH.sub.4).sub.3H(SO.sub.4).sub.2, LiHSO.sub.4, NaHSO.sub.4,
KHSO.sub.4, RbSO.sub.4, LiN.sub.2H.sub.5SO.sub.4,
NH.sub.4HSO.sub.4,
[0058] Phosphates such as Zr.sub.3(PO.sub.4).sub.4,
Zr(HPO.sub.4).sub.2, HZr.sub.2(PO.sub.4).sub.3,
UO.sub.2PO.sub.4.3H.sub.2O, H.sub.8UO.sub.2PO.sub.4,
Ce(HPO.sub.4).sub.2, Ti(HPO.sub.4).sub.2, KH.sub.2PO.sub.4,
NaH.sub.2PO.sub.4, LiH.sub.2PO.sub.4, NH.sub.4H.sub.2PO.sub.4,
CsH.sub.2PO.sub.4, CaHPO.sub.4, MgHPO.sub.4, HSbP.sub.2O.sub.8,
HSb.sub.3P.sub.2O.sub.14, H.sub.5Sb.sub.5P.sub.2O.sub.- 20,
[0059] Polyacids such as H.sub.3PW.sub.12O.sub.40.nH.sub.2O
(n=21-29), H.sub.3SiW.sub.12O.sub.40.nH.sub.2O (n=21-29),
H.sub.xWO.sub.3, HSbWO.sub.6, H.sub.3PMo.sub.12O.sub.40,
H.sub.2Sb.sub.4O.sub.11, HTaWO.sub.6, HNbO.sub.3, HTiNbO.sub.5,
HTiTaO.sub.5, HSbTeO.sub.6, H.sub.5Ti.sub.4O.sub.9, HSbO.sub.3,
H.sub.2MoO.sub.4
[0060] Selenites and arsenides such as
(NH.sub.4).sub.3H(SeO.sub.4).sub.2, UO.sub.2AsO.sub.4,
(NH.sub.4).sub.3H(SeO.sub.4).sub.2, KH.sub.2AsO.sub.4,
Cs.sub.3H(SeO.sub.4).sub.2, Rb.sub.3H(SeO.sub.4).sub.2,
[0061] Oxides such as Al.sub.2O.sub.3, Sb.sub.2O.sub.5, ThO.sub.2,
SnO.sub.2, ZrO.sub.2, MoO.sub.3
[0062] Silicates such as zeolites, zeolites(NH.sub.4+), sheet
silicates, network silicates, H-natrolites, H-mordenites,
NH.sub.4-analcines, NH.sub.4-sodalites, NH.sub.4-gallates,
H-montmorillonites
[0063] Acids such as HClO.sub.4, SbF.sub.5
[0064] Fillers such as carbides, in particular SiC,
Si.sub.3N.sub.4, fibers, in particular glass fibers, glass powders
and/or polymer fibers, preferably those based on polyazoles.
[0065] This membrane can also further comprise perfluorinated
sulfonic acid additives (0.1-20% by weight, preferably 0.2-15% by
weight, very particularly preferably 0.2-10% by weight). These
additives lead to a performance improvement, in the vicinity of the
cathode to an increase in the oxygen solubility and oxygen
diffusion and to a decrease in the adsorption of phosphoric acid
and phosphate on platinum. (Electrolyte additives for phosphoric
acid fuel cells. Gang, Xiao; Hjuler, H. A.; Olsen, C.; Berg, R. W.;
Bjerrum, N. J. Chem. Dep. A, Tech. Univ. Denmark, Lyngby, Den. J.
Electrochem. Soc. (1993), 140(4), 896-902, and perfluorosulfonimide
as an additive in phosphoric acid fuel cell. Razaq, M.; Razaq, A.;
Yeager, E.; DesMarteau, Darryl D.; Singh, S. Case Cent.
Electrochem. Sci., Case West. Reserve Univ., Cleveland, Ohio, USA.
J. Electrochem. Soc. (1989), 136(2), 385-90.)
[0066] Nonlimiting examples of persulfonated additives are:
Trifluoromethanesulfonic acid, potassium trifluoromethanesulfonate,
sodium trifluoromethanesulfonate, lithium
trifluoromethanesulfonate, ammonium trifluoromethanesulfonate,
potassium perfluorohexanesulfonate, sodium
perfluorohexanesulfonate, lithium perfluorohexanesulfonate,
ammonium perfluorohexanesulfonate, perfluorohexanesulfonic acid,
potassium nonafluorobutanesulfonate, sodium
nonafluorobutanesulfonate, lithium nonafluorobutanesulfonate,
ammonium nonafluorobutanesulfonate, cesium
nonafluorobutanesulfonate, triethylammonium
perfluorohexanesulfonate, perfluorosulfonimides and Nafion.
[0067] Furthermore, the membrane can further comprise additives
which scavenge (primary antioxidants) or destroy (secondary
antioxidants) the peroxide radicals generated by reduction of
oxygen in operation and thereby increase the life and stability of
the membrane and membrane electrode unit, as described in
JP2001118591 A2. The molecular structures of such additives and the
way in which they function are described in F. Gugumus in Plastics
Additives, Hanser Verlag, 1990; N. S. Allen, M. Edge Fundamentals
of Polymer Degradation and Stability, Elsevier, 1992; or H.
Zweifel, Stabilization of Polymeric Materials, Springer, 1998.
[0068] Nonlimiting Examples of Such Additives are:
[0069] bis(trifluoromethyl) nitroxide,
2,2-diphenyl-1-picrinylhydrazyl, phenols, alkylphenols, sterically
hindered alkylphenols such as Irganox, aromatic amines, sterically
hindered amines such as Chimassorb; sterically hindered
hydroxylamines, sterically hindered alkylamines, sterically
hindered hydroxylamines, sterically hindered hydroxylamine ethers,
phosphites such as Irgafos, nitrosobenzene,
methyl-2-nitrosopropane, benzophenone, benzaldehyde
tert-butyinitrone, cysteamine, melamines, lead oxides, manganese
oxides, nickel oxides, cobalt oxides.
[0070] The possible fields of use of the doped polymer membranes
according to the invention include, inter alia, use in fuel cells,
in electrolysis, in capacitors and in battery systems. Owing to
their property profile, the doped polymer membranes are preferably
used in fuel cells.
[0071] The present invention also relates to a membrane-electrode
unit comprising at least one polymer membrane according to the
invention. For further information on membrane-electrode units,
reference may be made to the specialist literature, in particular
the patents U.S. Pat. No. 4,191,618, U.S. Pat. No. 4,212,714 and
U.S. Pat. No. 4,333,805. The disclosure in the abovementioned
references [U.S. Pat. No. 4,191,618, U.S. Pat. No. 4,212,714 and
U.S. Pat. No. 4,333,805] regarding the structure and production of
membrane-electrode units and the electrodes, gas diffusion layers
and catalysts to be chosen is hereby incorporated by reference into
the present description.
[0072] In one variant of the present invention, the membrane can be
formed directly on the electrode rather than on a support. The
treatment in step D) can be shortened in this way, since the
membrane no longer has to be self-supporting. Such a membrane is
also subject matter of the present invention.
[0073] The present invention further provides an electrode provided
with a proton-conducting polymer coating based on polyazoles which
is obtainable by a process comprising the steps
[0074] A) Dissolution of the polyazole polymer in polyphosphoric
acid,
[0075] B) Heating of the solution obtainable as described in step
A) to temperatures of up to 400.degree. C., preferably up to
350.degree. C., in particular of up to 300.degree. C. under inert
gas,
[0076] C) Application of a layer to an electrode using the solution
of the polyazole polymer from step B), and
[0077] D) Treatment of the layer formed in step C).
[0078] The coating has a thickness of from 2 to 300 .mu.m,
preferably from 5 to 250 .mu.m, in particular from 10 to 100
.mu.m.
[0079] The above-described variants and preferred embodiments are
also applicable to this electrode, so that they will not be
repeated at this point.
[0080] An electrode which has been coated in this way can be
incorporated in a membrane-electrode unit which may, if desired,
comprise at least one polymer membrane according to the
invention.
[0081] In a further variant, a catalytically active layer can be
applied to the membrane of the invention and this can be joined to
a gas diffusion layer. For this purpose, a membrane is formed in
accordance with the steps A) to D) and the catalyst is applied.
These structures are also subject matter of the present
invention.
[0082] Furthermore, the formation of the membrane in accordance
with the steps A) to D) can also be carried out on a support or a
support film on which the catalyst is already present. After
removal of the support or the support film, the catalyst is located
on the membrane according to the invention. These structures are
also subject matter of the present invention.
[0083] The present invention likewise provides a membrane-electrode
unit which comprises at least one coated electrode and/or at least
one polymer membrane according to the invention in combination with
a further polymer membrane based on polyazoles or a polymer blend
membrane comprising at least one polymer based on polyazoles. In
the present context, a polyazole is a polymer comprising recurring
azole units of the formula (I) and/or (II), in particular of the
formula (III).
[0084] General Measurement Methods:
[0085] Method of Measuring the IEC
[0086] The conductivity of the membrane is dependent to a high
degree on the content of acid groups expressed by the ion exchange
capacity (IEC). To measure the ion exchange capacity, a specimen
having a diameter of 3 cm is stamped out and placed in a glass
beaker filled with 100 ml of water. The acid liberated is titrated
with 0.1 M NaOH. The specimen is subsequently taken out, excess
water is dabbed off and the specimen is dried at 160.degree. C. for
4 hours. The dry weight, m.sub.0, is then determined
gravimetrically to a precision of 0.1 mg. The ion exchange capacity
is then calculated from the consumption of 0.1 M NaOH to the first
titration end point, V.sub.1 in ml, and the dry weight, m.sub.0 in
mg, according to the following formula:
IEC=V.sub.1*300/m.sub.0
[0087] Method of Measuring the Specific Conductivity
[0088] The specific conductivity is measured by means of impedance
spectroscopy in a 4-pole arrangement in the potentiostatic mode
using platinum electrodes (wire, 0.25 mm diameter). The distance
between the current-collecting electrodes is 2 cm. The spectrum
obtained is evaluated using a simple model consisting of a parallel
arrangement of an ohmic resistance and a capacitor. The specimen
cross section of the membrane doped with phosphoric acid is
measured immediately before installation of the specimen. To
measure the temperature dependence, the measurement cell is brought
to the desired temperature in an oven and the temperature is
regulated via a Pt-100 resistance thermometer positioned in the
immediate vicinity of the specimen. After the desired temperature
has been reached, the specimen is held at this temperature for 10
minutes before commencement of the measurement.
EXAMPLES
[0089] Membrane Production
[0090] 10 g of polybenzimidazole (PBI) having an inherent viscosity
(IV) of 0.92 dl/g obtained from the manufacturing plant in Rock
Hill, USA, are placed in a 100 ml three-necked flask equipped with
a mechanical stirrer, nitrogen inlet and outlet. 90 g of
polyphosphoric acid (P.sub.2O.sub.5 content=83.4%, determined by
analysis) are added thereto. This mixture is heated to 270.degree.
C. and maintained at this temperature for 14 hours. The PBI polymer
dissolves completely in the PPA, but the 10% PBI/PPA solution is
very viscous. At this temperature, 33.33 g of an 85% phosphoric
acid are added. The mixture obtained in this way is cooled to
240.degree. C. over a period of 1 hour while stirring, forming a
homogeneous, pourable solution. The resulting 7.5% strength PBI
solution in 106.9% PPA is applied at 240.degree. C. by means of a
doctor blade to glass plates which have previously been heated to
100.degree. C. Films having a thickness of from 150 .mu.m and 200
.mu.m were applied by means of a doctor blade. These films were
then allowed to stand at room temperature under ambient conditions
for 3 days. Absorption of moisture from the air results in
hydrolysis of polyphosphoric acid to phosphoric acid. Excess
phosphoric acid is dabbed off and a mechanical stable membrane
consisting of the PBI/polyphosphoric acid/phosphoric acid system is
obtained.
[0091] To determine the inherent viscosity, part of the solution
after the heat treatment is precipitated by mixing with distilled
water. The resin-like product obtained in this way is filtered off,
washed three times with distilled water in a kneader, neutralized
with ammonia hydroxide, washed three more times with water and
subsequently dried at 120.degree. C. and 1 torr for 16 hours to
give a PBI powder. The PBI powder is dissolved at a concentration
of 0.4% by weight in 96% sulfuric acid and the inherent viscosity
is then determined by means of an Ubbelohde viscometer in a bath
maintained at 25.degree. C., giving a value of 1.68 dl/g.
[0092] Determination of the Membrane Properties
[0093] To determine the acid content, the membranes are placed in a
glass beaker filled with water and the acid liberated is titrated
against 0.1 molar sodium hydroxide solution. After the titration,
the membranes are dried at 150.degree. C. for 4 hours in a drying
oven. The dry weight m.sub.0 is then determined. The acid content,
measured as the ratio of the molar amount of H.sub.3PO.sub.4 per
repeating unit of polybenzimidazole (molar mass of PBI=308 mol/g),
is calculated from the amount of alkali consumed up to the
equivalence point and m.sub.0.
[0094] The specific conductivity is measured by means of impedance
spectroscopy in a 4-pole arrangement in the potentiostatic mode
using platinum electrodes (wire, 0.25 mm diameter). The distance
between the current-collecting electrodes is 2 cm. The spectrum
obtained is evaluated using a simple model consisting of a parallel
arrangement of an ohmic resistance and a capacitor. The specimen
cross section of the membrane doped with phosphoric acid is
measured immediately before mounting of the specimen. To measure
the temperature dependence, the measurement cell is brought to the
desired temperature in an oven and the temperature is regulated via
a Pt-100 resistance thermometer positioned in the immediate
vicinity of the specimen. After the temperature has been reached,
the specimen is maintained at this temperature for 10 minutes
before commencement of the measurement.
[0095] The properties of the membranes according to the invention
are summarized in table 1.
1 Membrane thickness Specific Mem- after doctor blade
n(H.sub.3PO.sub.4)/ Measurement conductivity brane coating [.mu.m]
n(PBI) temperature [S/cm] 1 150 13.2 25 0.115 40 0.099 60 0.074 80
0.081 100 0.101 120 0.118 140 0.126 160 0.128 2 200 14 25 0.115 40
0.087 60 0.071 80 0.080 100 0.100 120 0.115 140 0.124 160 0.126
* * * * *