CN101390244A - Liquid materials for use in electrochemical cells - Google Patents
Liquid materials for use in electrochemical cells Download PDFInfo
- Publication number
- CN101390244A CN101390244A CNA2005800092318A CN200580009231A CN101390244A CN 101390244 A CN101390244 A CN 101390244A CN A2005800092318 A CNA2005800092318 A CN A2005800092318A CN 200580009231 A CN200580009231 A CN 200580009231A CN 101390244 A CN101390244 A CN 101390244A
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- Prior art keywords
- liquid precursor
- electrode
- catalyst
- pfpe
- proton
- Prior art date
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- 239000011344 liquid material Substances 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 359
- 239000003054 catalyst Substances 0.000 claims abstract description 156
- 239000012705 liquid precursor Substances 0.000 claims abstract description 148
- 239000012528 membrane Substances 0.000 claims abstract description 146
- 239000007772 electrode material Substances 0.000 claims abstract description 133
- 239000000203 mixture Substances 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims description 280
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 80
- 230000008569 process Effects 0.000 claims description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- 239000000446 fuel Substances 0.000 claims description 64
- 238000000059 patterning Methods 0.000 claims description 58
- 229920000642 polymer Polymers 0.000 claims description 53
- 239000000178 monomer Substances 0.000 claims description 43
- 238000002360 preparation method Methods 0.000 claims description 43
- 239000012530 fluid Substances 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- 239000004020 conductor Substances 0.000 claims description 34
- 125000003118 aryl group Chemical group 0.000 claims description 33
- 238000012545 processing Methods 0.000 claims description 29
- -1 alkylol Chemical class 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
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- 239000011737 fluorine Substances 0.000 claims description 20
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- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
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- 125000003107 substituted aryl group Chemical group 0.000 claims description 13
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- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 6
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XETQTCAMTVHYPO-UHFFFAOYSA-N Isocamphan von ungewisser Konfiguration Natural products C1CC2C(C)(C)C(C)C1C2 XETQTCAMTVHYPO-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VFIJBTVGUHVPPW-UHFFFAOYSA-N [Br].C=C Chemical compound [Br].C=C VFIJBTVGUHVPPW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000777 acyl halide group Chemical group 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005115 alkyl carbamoyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000001361 allenes Chemical class 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
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- 238000005452 bending Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 229940125904 compound 1 Drugs 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 239000000806 elastomer Substances 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
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- DLEGDLSLRSOURQ-UHFFFAOYSA-N fluroxene Chemical compound FC(F)(F)COC=C DLEGDLSLRSOURQ-UHFFFAOYSA-N 0.000 description 1
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- YVXHZKKCZYLQOP-UHFFFAOYSA-N hept-1-yne Chemical compound CCCCCC#C YVXHZKKCZYLQOP-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
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- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
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- 125000003010 ionic group Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001127 nanoimprint lithography Methods 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ORQBXQOJMQIAOY-UHFFFAOYSA-N nobelium Chemical compound [No] ORQBXQOJMQIAOY-UHFFFAOYSA-N 0.000 description 1
- 125000005485 noradamantyl group Chemical group 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
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- 150000003217 pyrazoles Chemical class 0.000 description 1
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- 125000006850 spacer group Chemical group 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
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- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Inert Electrodes (AREA)
Abstract
Disclosed is the use of liquid precursor materials to prepare a processible polymeric electrolyte, which can be used to form a proton exchange membrane for use in an electrochemical cell. Also disclosed is the use of liquid precursor materials to prepare a processible catalyst ink composition, which can be conformally applied to a proton exchange membrane and a electrode material for use in an electrochemical cell. Also disclosed is the use of a photocurable perfluoropolyether (PFPE) material to form a microfluidic electrochemical cell.
Description
Cross-reference to related applications
The application based on and require the U.S. Provisional Patent Application the 60/538th submitted on January 23rd, 2004, No. 706 and the U.S. Provisional Patent Application the 60/538th submitted on January 23rd, 2004, No. 878 priority, the full content of these two pieces of patents is incorporated herein with the form of reference.
Government's rights and interests
The present invention is subsidizing N00014210185 number from research administration of naval and the U.S. government of the Science and Technology center project contract of National Science Foundation CHE-9876674 number carries out under supporting.U.S. government has certain right to the present invention.
Technical field
The present invention relates to be used for the fluent material of electrochemical cell.
List of abbreviations
AC=interchange
Ar=argon gas
℃=degree centigrade
Cm=centimetre
CSM=cure site monomer (cure site monomer)
G=gram
H=hour
HMDS=hexamethyldisiloxane
IL=imprint lithography
MCP=micro-contact printing
Me=methyl
MEA=membrane electrode assembly
MEMS=micro-electromechanical system
MeOH=methyl alcohol
The little molding of MIMIC=capillary
ML=milliliter
Mm=millimeter
Mmol=mM
M
n=number-average molecular weight
M.p.=fusing point
MW=milliwatt
NCM=nanometer contact molding
NIL=nano-imprint lithography
Nm=nanometer
Pd=palladium
PDMS=dimethyl silicone polymer
PEM=proton exchange membrane
PFPE=PFPE
PSEPVE=perfluor-2-(2-fluorine nyl ethoxy) propyl vinyl ether
PTFE=polytetrafluoroethylene
Little molding that SAMIM=solvent is auxiliary
SEM=scanning electron microscopy
Si=silicon
TFE=tetrafluoroethene
μ m=micron
UV=ultraviolet ray
W=watt
ZDOL=poly-(ptfe ring oxidative ethane-copolymerization-difluoro formaldehyde) α, the ω glycol
Background technology
Fuel cell is portable set, vehicle (comprising motor vehicle driven by mixed power), generator and aerospace and military safe, eco-friendly energy source.But because cost, size and shortage replace the demand immediately of present power supply (for example battery and gasoline or diesel internal combustion engine), the prior art of fuel cell does not also cause remarkable influence for main flow market.But the long-term needs of seeking alternative power supply have become obvious day by day.For example, gasoline and diesel internal combustion engine are harmful on environment.On the contrary, the accessory substance of fuel cell cleans, and only comprises water in some cases.
In addition, along with portable electric appts, for example cell phone, notebook computer and hand-hold type personal organiser (personal organizers) diminish, and to littler power supply, for example the demand of micro fuel cell becomes obvious.But present fuel cell technology typically needs to comprise the big fuel battery of expensive smooth proton exchange membrane (PEM).
In addition, consumer products need to work in the time that prolongs and the power supply that do not need to recharge.Micro fuel cell typically can provide longer lasting energy output under a fuel cassette.For example, be used for that the chemical fuel of micro fuel cell is reinforced once can to reach 10 times of battery to power devices.In addition, in case energy step-down only just can recover energy level by the alternative fuel box.
Most of fuel cells use tetrafluoroethene (TFE) and comprise the perfluorinated monomers of sulfonic acid group, for example copolymer of perfluor sulfonyl fluoride ethoxycarbonyl propyl vinethene (PSEPVE).A kind of can be used as in this copolymer
(E.I.duPont de Nemours andCo., Wilmington, Delaware, the U.S.) obtains, or similar commercially available material.Usually provide these materials to be used for subsequently use with the final form of film, for example to have the non-thermoplastic form of planar rectangular or square geometry.If film is flat and smooth, and is promptly patternless, catalyst layer also must be flat.In addition, this film typically must have accessible certain at least minimum thickness.In addition, power density or conductivity are common and thickness is proportional, and promptly film is thick more, and power density is low more.
In addition,
Lu etc., Electrochimica Acta, 49,821-828 (2003) has described silica-base material and has been used for micro direct methanol fuel battery.The direct fuel cell of silicon-base miniature is typically to make expensive and device rigidity, frangible consuming time.In addition, because the rigidity characteristics of material, in silica-base material, be difficulty or impossible in conjunction with starter gate valve.In addition,
Lu etc.The silicon based minisize direct carbinol fuel cell of describing has 1 the active area ratio to macroscopical area that approximates.
In addition, in present obtainable fuel cell technology, it is necessary having excellent contact between electrode, proton exchange membrane (PEM) and the catalyst.High power density relies on the conformal contact between electrode, catalyst and the PEM.New PEM of exploitation and new catalyst aspect have been put in more research, but in new catalyst ink Composition Aspects research seldom.Traditional catalyst ink or belt typically by the electrode material of the catalyst of for example platinum, for example carbon black and
The dispersion liquid of water and alcohol is formed.
In addition, present obtainable PEM is made up of single equivalent weight (EW) in this area, and this just causes the balance (trade-off) between power density and the methanol permeability.
Therefore, this area needs improved electrochemical cell, the micro fuel cell of power is provided, and needs improved electrochemical cell assembly particularly can for little, portable electric appts.
Summary of the invention
The invention describes and be used for electrochemical cell, for example the fluent material of fuel cell, chlor-alkali cell, storage battery (battery) etc.Therefore, in some embodiments, the invention provides a kind of polymer electrolyte composition and the method for preparing polymer dielectric.In some embodiments, described method comprises: 100% liquid precursor material of solidifying (solid) (a) is provided, and wherein said 100% liquid precursor material of solidifying comprises the polymerizable material of about 70 weight % to about 100 weight %; (b) handle described liquid precursor material, form polymer dielectric.
In some embodiments, described 100% liquid precursor material of solidifying comprises the precursor that is selected from proton-conducting material, proton-conducting material and the material in their combination.In some embodiments, described 100% liquid precursor material of solidifying comprises the material that is selected from monomer, oligomer, macromonomer, ionomer and their combination.In some embodiments, comprise one of at least functionalized PFPE (PFPE) material in described monomer, oligomer, macromonomer and the ionomer.
In some embodiments, described functionalized PFPE (PFPE) material comprises the skeleton structure that is selected from the following structure:
Wherein exist or do not have X, and when having X, comprise end-capping group, and n is the integer of 1-100.Therefore, in some embodiments, described functionalized PFPE material is selected from the following material:
Wherein R is selected from alkyl, substituted alkyl, aryl and substituted aryl, and wherein m and n each be the integer of 1-100 independently of one another.
In some embodiments, described ionomer is selected from sulfonic acid material and phosphoric acid material.In some embodiments, the sulfonic acid material comprises the derivative of sulfonic acid material.In some embodiments, the derivative of sulfonic acid material comprises the material of perfluor-2-(the 2-fluorine nyl ethoxy) propyl vinyl ether (PSEPVE) that contains following general formula:
Wherein q is the integer of 1-5.
In some embodiments, the derivative of sulfonic acid material comprises and is selected from following material:
Wherein:
Y is selected from-SO
2F and-SO
3H;
R
1Be selected from alkyl, substituted alkyl, hydroxyl, alkoxyl, fluorine-containing thiazolinyl, cyano group and nitro;
X
1Be selected from key, O, S, SO, SO
2, CO, NR
2And R
3
X
2Be selected from O, S and NR
2,
Wherein:
R
2Be selected from hydrogen, alkyl, substituted alkyl, aryl and substituted aryl; And
R
3Be selected from alkylidene, substituted alkylene, aryl and substituted aryl;
Ar is selected from aryl and substituted aryl;
B is 1, the inferior cyclobutyl of 2-perfluor;
T is the integer of 1-3;
M is 0 to 1000 integer;
P is the integer of 1-1000; And
Q is the integer of 1-5.
Therefore, in some embodiments, the invention provides the polymer dielectric that comprises 100% liquid precursor material of solidifying, wherein 100% liquid precursor material of solidifying comprises the polymerizable material of about 70 weight % to about 100 weight %.
In some embodiments, the invention provides the method for the polymer dielectric of preparation patterning, described method comprises:
(a) liquid precursor material is contacted with the ground of patterning, the ground of wherein said patterning has predetermined geometry and macro surface is long-pending; And
(b) handle described liquid precursor material, form the polymer dielectric of patterning.
In some embodiments, described liquid precursor material comprises the precursor that is selected from proton-conducting material, proton-conducting material and the material in their combination.In some embodiments, the polymer dielectric of patterning has greater than the long-pending surface area of the macro surface of patterning ground.
In some embodiments, the invention provides the method that preparation has the polymer dielectric of a plurality of equivalent weights, described method comprises:
(a) on ground, use first liquid precursor material with first equivalent weight;
(b) handle described first liquid precursor material, on ground, form the liquid precursor material that ground floor is handled;
(c) on the treated liquid precursor material of the ground floor on the ground, use second liquid precursor material with second equivalent weight; And
(d) handle described second liquid precursor material, form polymer dielectric with a plurality of equivalent weights.
In some embodiments, described method comprises uses the predetermined multiple liquid precursor material repeating step (c) with a plurality of equivalent weights to (d), forms the polymer dielectric with a plurality of equivalent weights.
In some embodiments, first liquid precursor material, second liquid precursor material and multiple liquid precursor material are selected from the precursor of proton-conducting material, proton-conducting material and their combination.In some embodiments, described first equivalent weight is greater than described second equivalent weight.In some embodiments, described second equivalent weight is greater than described a plurality of equivalent weights.Thereby, provide the equivalent weight gradient along the section of polymer dielectric.
The present invention also provides the method for formation membrane electrode assembly (MEA).In some embodiments, the method for described formation membrane electrode assembly (MEA) comprising:
(a) provide the proton exchange membrane of patterning;
(b) provide first catalyst material and second catalyst material;
(c) provide first electrode material and second electrode material;
(d) mode that is communicated with conduction is operationally settled described proton exchange membrane, described first and second catalyst materials and described first and second electrode materials, forms membrane electrode assembly.
In some embodiments, at least aly in first catalyst material and second catalyst material comprise accessible catalyst ink water composition.In some embodiments, described accessible catalyst ink water composition comprises liquid precursor material.In some embodiments, described accessible catalyst ink water composition conformally is administered on proton exchange membrane and electrode material any or both.
In some embodiments, the present invention's method of forming membrane electrode assembly comprises:
(a) provide first electrode material;
(b) provide second electrode material;
(c) settle described first electrode material and second electrode material in the spatial placement mode that between described first electrode material and second electrode material, forms spacing;
(d) arrange liquid precursor material in the spacing between described first electrode material and second electrode material; And
(e) handle described liquid precursor material, form membrane electrode assembly.
In some embodiments, described liquid precursor material is selected from the precursor of proton-conducting material, proton-conducting material and their combination.
The present invention also provides the method that forms electrochemical cell.In some embodiments, described method comprises:
(a) provide one deck PFPE (PFPE) material at least, it comprises at least one fluid channel;
(b) provide first electrode material and second electrode material;
(c) provide first catalyst material and second catalyst material;
(d) provide proton exchange membrane; And
(e) operationally settle the described PFPE of one deck at least material, described first electrode material, described second electrode material, described first catalyst material, described second catalyst material and described proton exchange membrane, form electrochemical cell.
In addition, in some embodiments, the invention provides the method for operation electrochemical cell.Therefore, electrochemical cell of the present invention can be used for operating portable electric appts (such as, but be not limited to portable electric generator, portable instrument), electric tool, electronic equipment (for example electronic equipment for consumption and Military Electronic Equipment), road or traffic sign, stand-by power supply and individual vehicle (for example automobile).
Therefore, an object of the present invention is to provide the new liquid material that is used for electrochemical cell.Can realize described purpose and other purpose wholly or in part by the present invention.
Describe below in conjunction with the description to accompanying drawing and most preferred embodiment, it is obvious that above-mentioned purpose of the present invention, others and purpose will become.
Description of drawings
Figure 1A and 1B provide the schematic diagram of the embodiment of the inventive method that is used to prepare proton exchange membrane.
Figure 1A is the schematic diagram of peg mould (peg mold), and it can interdigitation and can be used to form the mould (for example patterning ground) of patterning proton exchange membrane of the present invention.
Figure 1B is the schematic diagram of the proton exchange membrane for preparing in the peg mould of the interdigitation that provides from Figure 1A.
Fig. 2 A and 2B are the stereoscan photographs by the proton exchange membrane that comprises the sharkskin pattern (PEM) of the inventive method preparation.
Fig. 2 A is the stereoscan photograph that comprises the PEM of the present invention of sharkskin pattern before the hydrolysis.
Fig. 2 B is the stereoscan photograph that comprises the PEM of the present invention of sharkskin pattern after the hydrolysis.
Fig. 3 A and 3B are to use the electrode pair of patterning to form the schematic diagram of embodiment of the inventive method of proton exchange membrane of the present invention as mould.
Fig. 4 is the figure that is illustrated in the conductivity of the proton exchange membrane embodiment of the present invention that has 1900 equivalent weights under the condition of complete aquation.
Fig. 5 is the figure that is illustrated in the conductivity of the proton exchange membrane embodiment of the present invention that has 1250 equivalent weights under the condition of complete aquation.
Fig. 6 is the figure that is illustrated in the conductivity of the proton exchange membrane embodiment of the present invention that has 850 equivalent weights under the condition of complete aquation.
Fig. 7 is the figure that is illustrated in the conductivity of the proton exchange membrane embodiment of the present invention that has 660 equivalent weights under the condition of complete aquation.
Fig. 8 is the figure that is illustrated in the conductivity of the proton exchange membrane embodiment of the present invention that has 550 equivalent weights under the condition of complete aquation.
Fig. 9 A and 9B are the schematic diagrames that comprises proton exchange membrane of the present invention (PEM) embodiment of the fluent material that changes equivalent weight, and its section along PEM provides the equivalent weight gradient.
Figure 10 A and 10B are the schematic diagrames of embodiment that is used for forming the inventive method of catalyst ink belt.
Figure 10 A is the schematic diagram of embodiment that is used on the plane electrode material forming the inventive method of catalyst ink belt.
Figure 10 B is the schematic diagram of embodiment that is used on the proton exchange membrane of patterning forming the inventive method of catalyst ink belt.
Figure 11 A-11C is the schematic diagram that is used for the embodiment of the inventive method of the proton exchange membrane of accessible catalyst ink water composition and electrode material application patternization.
Figure 11 A is the schematic diagram of an embodiment of the inventive method, wherein uses the PEM of accessible catalyst ink water composition conformal spreading patterning, then with the electrode material coating, thus the planar surface of formation electrode material.
Figure 11 B is the schematic diagram of an embodiment of the inventive method, wherein uses the PEM of accessible catalyst ink water composition conformal spreading patterning, then uses the electrode material conformal spreading, thereby forms the conformal surface of electrode material.
Figure 11 C is the schematic diagram of an embodiment of the inventive method, wherein with the PEM of accessible catalyst ink water composition conformal spreading patterning to form the planar surface of accessible catalyst ink water composition, then use the electrode material conformal spreading, to form the planar surface of electrode material.
Figure 12 A and 12B are to use the stereoscan photograph of method of electrospraying with the embodiment of the patterning PEM of the present invention of catalyst conformal spreading.
Figure 13 is to use the stereoscan photograph of vapor deposition method with the embodiment of the patterning PEM of the present invention of catalyst conformal spreading.
Figure 14 A and 14B are the schematic diagrames of the embodiment of membrane electrode assembly of the present invention.
Figure 14 A is the schematic diagram of the embodiment of the three-dimensional films electrode assemblie of the present invention (MEA) with conformal catalyst cupport made from three-dimensional proton exchange membrane (PEM).
Figure 14 B is the schematic diagram of embodiment with two-dimensional electrode of the present invention of non-conformal catalyst cupport.
Figure 15 is from three-dimensional proton exchange membrane (PEM) and the schematic diagram with embodiment of the three-dimensional films electrode assemblie of the present invention (MEA) that the three-diemsnional electrode of conformal catalyst cupport makes.
Figure 16 has described and has been used for the photoetching method of patterned electrodes material (for example carbon black).
Figure 17 A and 17B are the schematic diagrames of the embodiment of microfluid fuel cell of the present invention.
Figure 17 A is the cutaway view of fuel cell embodiment of the present invention.
Figure 17 B is the plane graph of fuel cell embodiment of the present invention.
Figure 18 A-18C describes a series of schematic end view that comprise PFPE (PFPE) the patterns of material layer formation process of fluid channel of the present invention.
Embodiment
The invention describes at electrochemical cell, for example use fluent material in fuel cell, chlor-alkali cell, the storage battery.Therefore, the invention describes and be used to prepare the polymer dielectric (for example proton exchange membrane) that is used for electrochemical cell, comprise the fluent material of proton exchange membrane with equivalent weight gradient.The present invention has also described the improved electrochemical cell technology in conjunction with patterned film and electrode.In addition, the invention describes the fluent material that is used for preparing membrane electrode assembly, wherein between electrochemical cell assembly, represented the conformal contact that strengthens.Therefore, the present invention has also described the fluent material that is used for preparing the accessible catalyst ink water composition that is used for electrochemical cell.In addition, the invention describes the photocuring PFPE that is used for making the microfluidic device that uses in the electrochemical cell (for example micro direct methanol fuel battery and hydrogen fuel cell).The present invention has also described the method for operation electrochemical cell.
Now with reference to embodiment that has represented representative embodiment and accompanying drawing the present invention is described more fully hereinafter.But, the embodiment that the present invention can embody and should not be interpreted as being limited to herein and proposed with different form.On the contrary, it is in order thoroughly and all sidedly to describe the present invention that these embodiments are provided, and intactly passes on the scope of embodiment to those skilled in the art.
Unless otherwise defined, the theme one of ordinary skill in the art common sense described of all technology used herein and scientific terminology and the present invention has an identical meaning.The full content of all publications, patent application, patent and other list of references of mentioning herein all is incorporated herein with the form of reference.
In whole specification and claim, chemical formula that provides or title will contain all optics and stereoisomer, and the racemic mixture that has these isomers and mixture.
I.
Liquid precursor material
The invention describes accessiblely, promptly can form different shapes or can meet different shapes, and can be used for preparing the liquid dumpable precursor material of high surface PEM.In some embodiments, as this paper points out in more detail below, can come patterning by the ground (for example mould) of patterning and handle liquid precursor material (such as, but be not limited to being solidified into solid), thus the PEM of formation patterning.
Term used herein " 100% solidify liquid precursor material " refers to wherein when handling (for example curing) basically all liquid polymer precursor materials of polymerization of all components.Therefore, in some embodiments, " 100% liquid precursor material of solidifying " is substantially free of unpolymerized material.This character of " 100% solidify liquid precursor material " makes this material be different from the solution or the dispersion liquid of liquid precursor material well known in the art, and wherein said fluent material can comprise about 80 weight % to the solvent of about 98 weight % or other polymeric material not.For instance, the perfluoro fluid composition of the commonly used preparation amberplex in a kind of this area comprise about 2 weight % to the polymeric material of about 18 weight % and about 82 weight % to about 98 weight % can not polymerization solvent.Referring to No. the 4th, 433,082, the United States Patent (USP) of authorizing Grot, this patent full content is incorporated herein with the form of reference.
Therefore, in some embodiments, 100% fluent material that solidifies comprises the polymerizable material of about 70 weight % to about 75 weight %.In some embodiments, 100% fluent material that solidifies comprises the polymerizable material of about 75 weight % to about 80 weight %.In some embodiments, 100% fluent material that solidifies comprises the polymerizable material of about 80 weight % to about 85 weight %.In some embodiments, 100% fluent material that solidifies comprises the polymerizable material of about 85 weight % to about 90 weight %.In some embodiments, 100% fluent material that solidifies comprises the polymerizable material of about 90 weight % to about 95 weight %.In some embodiments, 100% fluent material that solidifies comprises the polymerizable material of about 95 weight % to about 98 weight %.In some embodiments, 100% fluent material that solidifies comprises the polymerizable material of about 98 weight % to about 100 weight %.Therefore, in some embodiments, 100% fluent material that solidifies comprises the polymerizable material of about 70 weight % to about 100 weight %.
In addition, in some embodiments, liquid precursor material comprises fluoro system (fluorinated system).In some embodiments, the fluoro system comprises PFPE (PFPE) material.In some embodiments, the PFPE material comprises the material of vinyl-functional, including, but not limited to the metering system vinyl acetate.
In some embodiments, liquid precursor material comprises the material that improves proton conductivity, comprises vinethene, for example perfluor-2-(2-fluorine nyl ethoxy) propyl vinyl ether PSEPVE).Term used herein " proton-conducting material " refers to that portion within it can move the material of proton.For example, in some embodiments, proton is moved to negative electrode by proton-conducting material from anode.For instance, measure proton conductivity, and the typical case provides with the unit of Siemens/cm (S/cm) by interchange well known in the art (AC) impedance method.This proton-conducting material typically has the proton conductivity greater than about 0.01S/cm.
In some embodiments, liquid precursor material comprises other the material of regulating material physical properties, comprises permeability, wetability, hot strength, toughness, the pliability of modulus, methyl alcohol and other liquid, and thermal property particularly.The example of synthetic method for preparing liquid precursor material disclosed herein is referring to embodiment 1-6.
Therefore, in some embodiments, the described method for preparing polymer dielectric comprises:
(a) provide 100% liquid precursor material of solidifying, wherein 100% liquid precursor material of solidifying comprises the polymerizable material of about 70 weight % to about 100 weight %; And
(b) handle described 100% liquid precursor material of solidifying, form polymer dielectric.
In some embodiments, 100% liquid precursor material of solidifying comprises the precursor of proton-conducting material, proton-conducting material and their combination.
In some embodiments, 100% liquid precursor material of solidifying comprises the material that is selected from monomer, oligomer, macromonomer, ionomer and their combination.
Term used herein " monomer " refers to pass through polymerization, thereby is basic structure contribution formation unit, the i.e. molecule of atom, atomic group and/or atomic radical of big molecule or polymer.Term " oligomer " refers to the molecule that molecular weight is medium relatively, and its structure comprises a small amount of a plurality of formation unit that come from the molecule of lower relative molecular weight.Term " big molecule " refers to big molecule or polymer, and it comprises can make big molecule as monomer and make monomeric unit to final big molecule or the contributive reactive terminal group of polymer chain.Term " ionomer " refers to that wherein a plurality of formations unit comprises the big molecule of ionogen, ionic group and their combination.
In some embodiments, comprise one of at least functionalized PFPE (PFPE) material in described monomer, oligomer, macromonomer and the ionomer.In some embodiments, functionalized PFPE (PFPE) material comprises the skeleton structure that is selected from the following structure:
With
Wherein exist or do not have X, and when having X, comprise end-capping group, and n is the integer of 1-100.
In some embodiments, functionalized PFPE material is selected from the following material:
Wherein R is selected from alkyl, substituted alkyl, aryl and substituted aryl; And wherein m and n each be the integer of 1-100 independently of one another.
In some embodiments, functionalized PFPE material has following structure:
In some embodiments, ionomer is selected from sulfonic acid material and phosphoric acid material.In some embodiments, ionomer comprises derivative, the phosphonyl group of derivative, hydroxy-acid group, the hydroxy-acid group of sulfonic acid group, sulfonic acid group, derivative, phosphate group, the derivative of phosphate group and/or their combination of phosphonyl group.
In some embodiments, the sulfonic acid material comprises the derivative of sulfonic acid material.In some embodiments, the sulfonic acid material comprises the material of perfluor-2-(the 2-fluorine nyl ethoxy) propyl vinyl ether (PSEPVE) that contains following general formula:
Wherein q is the integer of 1-5.
In some embodiments, the derivative of sulfonic acid material comprises and is selected from following material:
With
Wherein:
Y is selected from-SO
2F and-SO
3H;
R
1Be selected from alkyl, substituted alkyl, hydroxyl, alkoxyl, fluorine-containing thiazolinyl, cyano group and nitro;
X
1Be selected from key, O, S, SO, SO
2, CO, NR
2And R
3
X
2Be selected from O, S and NR
2,
Wherein:
R
2Be selected from hydrogen, alkyl, substituted alkyl, aryl and substituted aryl; And
R
3Be selected from alkylidene, substituted alkylene, aryl and substituted aryl;
Ar is selected from aryl and substituted aryl;
B is 1, the inferior cyclobutyl of 2-perfluor;
T is the integer of 1-3;
M is 0 to 1000 integer;
P is the integer of 1-1000; And
Q is the integer of 1-5.
In some embodiments, Y is-SO
2F.In some embodiments, Y is-SO
3H.
Therefore, in some embodiments, ionomer can comprise commercially available acid material, for example
(E.I.duPont de Nemours and Co., Wilmington, Delaware, the U.S.) or materials similar, including, but not limited to
(DowChemical Company, Midland, Michigan, the U.S.),
(AsahiChemical Industry Co., Tokyo, Japan),
(Ballard AdvancedMaterials, Burnaby, British Columbia, Canada) is perhaps as authorizing
Mao etc.No. the 6th, 559,237, United States Patent (USP) described in acid functionalization the inferior cyclobutyl polymer of perfluor and as authorizing
Hamrock etc.No. the 6th, 833,412, United States Patent (USP) described in the fluorinated polymer of acid functionalization, the full content of every piece of patent is incorporated herein with the form of reference.
Term used herein " alkyl " refers to C
1-20The linearity of (comprising end value) (i.e. " straight chain "), side chain or ring-type, saturated or to small part the hydrocarbon chain of unsaturated and unsaturated fully in some cases (being thiazolinyl and alkynyl), comprise methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, amyl group, hexyl, octyl group, vinyl, acrylic, cyclobutenyl, pentenyl, hexenyl, octenyl, butadienyl, propinyl, butynyl, pentynyl, hexin base, heptyne base and allene base for instance." side chain " refers to the alkyl that wherein rudimentary alkyl (for example methyl, ethyl or propyl group) is connected with linear alkyl chain." low alkyl group " refers to have 1 to about 8 carbon atoms, and for example the alkyl of 1,2,3,4,5,6,7 or 8 carbon atom (is C
1-8Alkyl)." senior alkyl " refers to have about 10 to about 20 carbon atoms, for example alkyl of 10,11,12,13,14,15,16,17,18,19 or 20 carbon atoms.In certain embodiments, " alkyl " is meant C especially
1-8Straight chained alkyl.In other embodiments, " alkyl " is meant C especially
1-8Branched alkyl.
Alkyl can randomly replace with one or more alkyl substituents that can be identical or different.Term " alkyl substituent " is including, but not limited to alkyl, halogen, virtue amino, acyl group, hydroxyl, aryloxy group, alkoxyl, alkylthio group, arylthio, alkoxy aryl, alkylthio-aryl, carboxyl, alkoxy carbonyl group, oxo and cycloalkyl.Can randomly insert nitrogen-atoms one or more oxygen, sulphur or replacement or unsubstituted along alkyl chain, wherein the substituting group of nitrogen is hydrogen, low alkyl group (being also referred to as " alkyl amino alkyl " herein) or aryl.
" ring-type " and " cycloalkyl " refers to have about 3 to about 10 carbon atoms, for example non-fragrant list or the multi-loop system of 3,4,5,6,7,8,9 or 10 carbon atoms.Cycloalkyl can randomly be that part is undersaturated.Cycloalkyl can also randomly replace with alkyl substituent defined herein, oxygen and/or alkylidene.Can randomly insert one or more oxygen, sulphur or replacement or unsubstituted nitrogen-atoms along the cycloalkyl chain, wherein the substituting group of nitrogen is hydrogen, low alkyl group or aryl, and heterocyclic group is provided thus.Representational monocyclic cycloalkyl ring comprises cyclopenta, cyclohexyl and suberyl.The polycyclic naphthene basic ring comprises adamantyl, octahydro naphthyl, decahydronaphthalenes, camphor, camphane and removes first adamantyl (noradamantyl).
" alkylidene " refers to have 1 to about 20 carbon atoms, for example the straight or branched divalence aliphatic alkyl of 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 carbon atom.Alkylidene can be straight chain, side chain or ring-type.Alkylidene can also randomly be undersaturated and/or replace with one or more " alkyl substituent ".Can randomly insert nitrogen-atoms one or more oxygen, sulphur or replacement or unsubstituted (being also referred to as " alkyl amino alkyl " herein) along alkylidene, wherein the nitrogen substituting group is foregoing alkyl.The example of alkylidene comprises methylene (CH
2-), ethylidene (CH
2-CH
2-), propylidene ((CH
2)
3-), cyclohexylene (C
6H
10-) ,-CH=CH-CH=CH-,-CH=CH-CH
2-,-(CH
2)
q-N (R)-(CH
2)
r-, wherein q and r each be from 0 to about 20 integer independently, for example 0,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20, and R is hydrogen or low alkyl group, methylene dioxy base (O-CH
2-O-) and ethylidene dioxy base (O-(CH
2)
2-O-).Alkylidene can have about 2 to about 3 carbon atoms and can have 6-20 carbon atom.
Term used herein " aryl " refers to aromatic substituent, its can be single aromatic rings or condense together, multi-aromatic ring covalently bound or that be connected with the shared group of for example methylene or ethylidene part.Shared linking group can also be carbonyl (for example in benzophenone) or oxygen (for example in diphenyl ether) or nitrogen (for example in diphenylamines).Term " aryl " specifically comprises heterocyclic aromatic compounds.Aromatic rings can comprise phenyl, naphthyl, xenyl, diphenyl ether, diphenylamines and benzophenone especially.In special embodiment, term " aryl " means and comprises about 5 to about 10 carbon atoms, the ring-type aromatic rings of 5,6,7,8,9 or 10 carbon atoms for example, and comprise 5-and 6-person's hydrocarbon and heteroaromatic ring.
Aryl can randomly replace with one or more aryl substituents that can be identical or different; wherein " aryl substituent " comprise alkyl, aryl, aralkyl, hydroxyl, alkoxyl, aryloxy group, alkoxy aryl, carboxyl, acyl group, halogen, nitro, alkoxy carbonyl, aryloxycarbonyl, aromatic alkoxy carbonyl, acyloxy, acylamino-, aromatic acylamino, carbamoyl, alkyl-carbamoyl, dialkyl amido formoxyl, arylthio, alkylthio group, arlydene and-NR ＇ R ＂, wherein R ＇ and R ＂ each be hydrogen, alkyl, aryl and aralkyl independently.
The instantiation of aryl is including, but not limited to cyclopentadienyl group, phenyl, furans, thiophene, pyrroles, pyrans, pyridine, imidazoles, benzimidazole, isothiazole, isoxazole, pyrazoles, pyrazine, triazine, pyrimidine, quinoline, isoquinolin, indoles, carbazole etc.
Term " arlydene " refers to remove the divalent group that hydrogen atom comes from mononuclear aromatic or polycyclic aromatic hydrocarbons (PAH) by two carbon atoms from aromatic rings." arlydene " examples of groups is including, but not limited to 1,2-phenylene, 1,3-phenylene and 1,4-phenylene.
Term used herein " substituted alkyl ", " cycloalkyl of replacement ", " substituted alkylene ", " substituted aryl " and " arlydene of replacement " comprise as defined herein alkyl, alkylidene and aryl, and wherein one or more atoms of alkyl, alkylidene, aryl or arlydene or functional group are replaced by another atom or functional group's (for example comprising halogen, aryl, alkyl, alkoxyl, hydroxyl, nitro, amino, alkylamino, dialkyl amido, sulfate radical and sulfydryl).
" alkoxyl " or " alkoxyalkyl " refers to alkyl-O-group, and wherein alkyl as previously described.Term used herein " alkoxyl " can refer to C
1-20(comprising end value) straight chain, side chain or ring-type, saturated or undersaturated oxygen-hydrocarbyl chain for example comprise methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, tert-butoxy and amoxy.
Term used herein " halogen ", " halide " or " halogen " refer to fluorine, chlorine, bromine and iodine group.
Term " hydroxyl " refers to-the OH group.
Term " hydroxyalkyl " refers to usefulness-OH group substituted alkyl.
Term " nitro " refers to-NO
2Group.
In some embodiments, the processing of precursor material comprises and is selected from following processes: (a) solidification process; (b) chemical modification process; (c) process and (d) combination of these processes of formation network.In some embodiments, described solidification process comprises the process that is selected from thermal process, photochemistry and the irradiation process.In some embodiments, irradiation process comprises uses the radiation exposure liquid precursor material, and wherein said ray is selected from gamma-rays and electron beam.In some embodiments, chemical modification process comprises cross-linking process.The RADIATION DECOMPOSITION method of fluoropolymer (comprising the PFPE material) exists
J.S.Forsythe etc., Prog.Polym.Sci., 25,101-136 provides in (2000), and document full content is incorporated herein with the form of reference.
In addition,
MaoDeng the open WO 99/61141 of PCT international application described to make by the following method and be applicable to for example method of the cross-linked polymer of the ion-conductive membranes of proton exchange membrane: (a) use, or (b) use in conjunction with the crosslinked polymer of the crosslinking agent of two or more amide groups with acid amides side group in conjunction with the crosslinked polymer of the crosslinking agent of two or more acyl halide groups with acyl halide side group.In addition,
Buchi etc., J.Electrochem.Soc., 142 (9), 3004 (1995) disclose by the crosslinked polyolefin-polystyrene copolymer of sulfonation and have prepared proton exchange membrane, and this copolymer is crosslinked by adding divinylbenzene between polymerization period.Authorize
Helmer-MetzmannDeng United States Patent (USP) method with the cross-linked aromatic polyether ketone of the crosslinking agent that comprises amine functional group is disclosed for the 5th, 438, No. 082.In addition, authorize
EhrenbergDeng No. the 5th, 468,574, United States Patent (USP) and
GrahamDeng the open WO97/19 of PCT international application, 480 some sulfonated polymers when disclosing heating will be between sulfonic acid group direct Cheng Jian, but this method shows the sacrifice sulfonic acid group, thereby cause loss acid in the film.Above-mentioned patent, document and disclosed patent application full content are incorporated herein with the form of reference.
Therefore, in some embodiments, the invention provides the polymer dielectric of 100% liquid precursor material of solidifying that comprises definition as mentioned, wherein 100% liquid precursor material of solidifying comprises the polymerizable material of about 70 weight % to about 100 weight %
In some embodiments, polymer dielectric of the present invention has equivalent weight, and wherein said equivalent weight is selected from less than about 1500 and greater than about 1000 equivalent weight, less than about 1000 and greater than about 800 equivalent weight, less than about 800 and greater than in about 500 equivalent weight and the 500 following equivalent weights.
In addition, in some embodiments, the invention provides the electrochemical cell that comprises from the polymer dielectric of the 100% liquid precursor preparation of solidifying.In some embodiments, described electrochemical cell is selected from fuel cell, chlor-alkali cell and storage battery.
In addition, when relative humidity is high, for example about 90% o'clock,
With other PEM material property the best.Alcohol is incorporated into
Make material more hydrophilic in the class material, this can cause at conductivity good under the lower relative humidity and/or the fluid loss that reduces under higher temperature.An example is provided in the route 11, and it provides uses the vinyl acetate polyisocyanate polyaddition
The method of class material component.Simple hydrolysis changes into alcohol with acetate, obtains sulfonic acid group simultaneously on the proton conduction compound.Fluoridizing after on the material to provide chemistry and thermal stability to perfluorinated material.
Be not subjected to any specific theory, the high conductance that it is believed that material of the present invention come from basically with
In the different proton conduction mechanism that works.According to maximum reports, for example referring to
Mauritz, K.A. and Moore, R.B., Chem.Rev., 104,4535-4585 (2004),
Pattern can be regarded as isolated bunch of the acid groups that is embedded in the polytetrafluoroethylene class parent.Proton can bunch in from the acid groups to the acid groups, jump, but for proton transmit on macroscopic view by PEM, it must pass hydrophilic channel with the form of hydrogen ion and bunch moves to the next one bunch from an acid.That is, in order to make
Be the height proton-conducting, need have the threshold values of the water yield.In order to make
Be the height proton-conducting, require its be hydration (referring to
Mauritz, K.A. And Moore, R.B., Chem.Rev., 104,4535-4585 (2004)), use being higher than under the temperature of water boiling point
During base fuel battery, this requirement has caused actual implementation barrier.In addition, be not subjected to any specific theory, it is believed that with the crosslinked liquid precursor of the present invention of PEM in the very high acid content that realizes form the acidic group continuum, these continuums are in the proton skip distance each other.So, proton can transmit on macroscopic view by film, and does not need and business level
Perhaps equivalent weight〉any other relevant water content of PEM material of 550.
In a word, material of the present invention can be used for traditional electrochemical cell application, and for example automobile is used, and the compact power that for example is used for electronic equipment.In some embodiments, material of the present invention at high temperature shows improved mechanical stability.In some embodiments, material of the present invention shows the permeability of reduction to the alkylol of for example methyl alcohol.In some embodiments, material of the present invention provides electrochemical cell performance and the hydrophilic increase of proton exchange membrane that increases under lower relative humidity.
II.
The method of the proton exchange membrane of preparation patterning
In some embodiments, the invention provides the method for the proton exchange membrane of preparation patterning.A this embodiment is provided among Figure 1A-1B.
With reference now to Figure 1A,, the ground of pattern is provided, for example mould 100.Mould 100 can comprise the material that is selected from inorganic material, organic material and their combination.In some embodiments, mould 100 has predetermined geometry 102, and wherein Yu Ding geometry 102 has macroscopical area 104.For instance as shown in Figure 1A, predetermined geometry 102 comprises the rectangle ground 106 with first plane surface 108, and wherein said first plane surface 108 further comprises a plurality of architectural features of representing as a plurality of pegs that stretch out 110 from first plane surface 108 in Figure 1A.
In addition, persons skilled in the art will be understood described a plurality of architectural feature 110 and can take any form when reading the disclosure of invention, including, but not limited to peg, groove nail (fluted peg), curling cylinder, pattern, wall and cross one another surperficial (not shown).Therefore, the proton exchange membrane for preparing by the inventive method can be made into various geometries, can have a large amount of passages and/or can comprise surface area control or variable.
In some embodiments, long-pending the comparing of the proton exchange membrane by the inventive method preparation and " macro surface " has bigger " active surface " and amasss.Therefore, in some embodiments, predetermined geometry 102 comprises the structure 110 of a plurality of surface areas greater than macroscopical area 104 of mould 100.In some embodiments, the surface area 112 of a plurality of structures 110 be mould 100 macro surface long-pending 104 at least about twice to about 100 times.In some embodiments, Yu Ding geometry 102 comprises the structure 110 of a plurality of surface areas 112 for the twice at least of the macro surface long-pending 104 of mould 100.In some embodiments, Yu Ding geometry 102 comprises at least five times the structure 110 of a plurality of surface areas 112 for the macro surface long-pending 104 of mould 100.In some embodiments, Yu Ding geometry 102 comprises at least 20 times the structure 110 of a plurality of surface areas 112 for the macro surface long-pending 104 of mould 100.In some embodiments, Yu Ding geometry 102 comprises at least 80 times the structure 110 of a plurality of surface areas 112 for the macro surface long-pending 104 of mould 100.
With reference now to Figure 1A and 1B,, liquid precursor material 114 is contacted with mould 100.Liquid precursor material 114 can comprise any above disclosed liquid precursor material, and promptly liquid precursor material can comprise the precursor of proton-conducting material, proton-conducting material and their combination.By processing procedure T
rHandle liquid precursor material 114, form the liquid precursor material 116 of the processing shown in Figure 1B.
In some embodiments, processing procedure T
rComprise in process, solvent evaporation process and their combination that is selected from solidification process, chemical modification process, formation network.In some embodiments, described solidification process comprises the process that is selected from thermal process, photochemistry and the irradiation process.In addition, in some embodiments, irradiation process comprises uses the radiation exposure fluent material, and wherein said ray is selected from gamma-rays and electron beam.In some embodiments, chemical modification process comprises cross-linking process.
With reference now to Figure 1B,, from mould 100, to remove the liquid precursor material 116 of processing, thereby (freestanding) proton exchange membrane 118 of self-supporting is provided, it comprises a plurality of and a plurality of architectural features 110 corresponding structure features 120 mould 100.In some embodiments, a plurality of structures 110 and 120 have the size 122 less than 10 millimeters.In some embodiments, a plurality of structures 110 and 120 have the size 122 less than 1 millimeter.In some embodiments, a plurality of structures 110 and 120 have the size 122 less than 100 microns.In some embodiments, a plurality of structures 110 and 120 have the size 122 less than 10 microns.In some embodiments, a plurality of structures 110 and 120 have the size 122 less than 1 micron.In other words, in some embodiments, the single structure that comprises a plurality of structures 110 and 120 can have size from less than about 10 millimeters to less than the height of about 1 micrometer range and/or size from less than about 10 millimeters to width less than about 1 micrometer range.
Therefore, in some embodiments, the invention provides the method for the polymer dielectric of preparation patterning, described method comprises:
(a) liquid precursor material is contacted with the ground of patterning, the ground of wherein said patterning has predetermined geometry and macro surface is long-pending; And
(b) handle described liquid precursor material, form the polymer dielectric of patterning.
In some embodiments, liquid precursor material comprises the precursor that is selected from proton-conducting material, proton-conducting material and the material in their combination.
In some embodiments, the ground of patterning comprises the material that is selected from inorganic material, organic material and their combination.
In some embodiments, Yu Ding geometry comprises nonplanar geometry.In some embodiments, nonplanar geometry has preliminary dimension, and this size is selected from less than about 10 millimeters and greater than about 1 millimeter size, less than about 1 millimeter and greater than about 100 microns size, less than about 100 microns and greater than about 10 microns size, less than about 10 microns and greater than about 1 micron size and less than the feature in about 1 micron size.
In some embodiments, Yu Ding geometry is by catalyst layer with one of comprise in the electrode material of membrane electrode assembly and to limit.In some embodiments, Yu Ding geometry is limited by membrane electrode assembly.In some embodiments, Yu Ding geometry comprises the structure that is selected from pattern, peg, wall, cross one another surface and the curling cylinder.
In some embodiments, Yu Ding geometry comprises that surface area is greater than the long-pending structure of the macro surface of the ground of patterning.In some embodiments, the surface area of described structure be the ground macro surface of patterning long-pending at least about twice to about 100 times.
In some embodiments, the processing of liquid precursor material comprises the process that is selected from the following process: (a) solidification process; (b) chemical modification process; (c) process of formation network; (d) solvent evaporation process; And (e) their combination.
Therefore, in some embodiments, the invention provides proton exchange membrane by the patterning of the inventive method preparation.In some embodiments, the proton exchange membrane of patterning comprises the material with equivalent weight, and wherein said equivalent weight is selected from less than about 1500 and greater than about 1000 equivalent weight, less than about 1000 and greater than about 800 equivalent weight, less than about 800 and greater than in about 500 equivalent weight and the 500 following equivalent weights.
In some embodiments, the invention provides the electrochemical cell that comprises patterning proton exchange membrane of the present invention.In some embodiments, described electrochemical cell is selected from fuel cell, chlor-alkali cell and the storage battery.
Example by the proton exchange membrane of the inventive method preparation is provided among Fig. 2 A and the 2B, and it has represented to have before the hydrolysis scanning electron micrograph that has the PEM of sharkskin pattern after the scanning electron micrograph of PEM of sharkskin pattern and the hydrolysis respectively.Prepare the sharkskin pattern as described in example 7 above.The characteristic size of sharkskin pattern, structure promptly recited above is about 2 microns width and about 8 microns height in this specific embodiment.By using described sharkskin pattern, the surface area of the PEM of patterning is about 5 times of surface area of the flat not patterning PEM with identical macro-size.Shown in the scanning electron micrograph that provides among Fig. 2 A, obtained the architectural feature of high-fidelity by the inventive method.In addition, shown in the scanning electron micrograph that provides among Fig. 2 B, pattern expands after the hydrolysis of PEM experience, but architectural feature is still significantly.
In some embodiments, the geometry of the predetermined geometry of mould 100 (for example element 102 of Figure 1A) and the PEM that wherein forms is limited by the catalyst belt (tie layer) (being provided in the following texts and pictures 10) and/or the electrode material of membrane electrode assembly.In addition, because liquid precursor material of the present invention, for example the liquid precursor material 114 of Figure 1A is a liquid, so it is dumpable.Therefore, liquid precursor material 114 can be poured in the ready-made structure, for example the structure that limits by electrode material.
For instance, with reference now to Fig. 3 A and 3B, operationally settle first electrode material 300 and second electrode material 302 so that produce the spatial placement mode in gap 304 therebetween.Liquid precursor material 306 is poured in the gap 304.Liquid precursor material 306 can comprise any above-mentioned disclosed liquid precursor material.Then, by processing procedure T
rHandle liquid precursor material 306, form the proton exchange membrane 308 on the position of function that is retained in some embodiments between first electrode material 300 and second electrode material 302.Therefore, in some embodiments, for example 306 liquid precursor material is directly injected preformed hole, for example in the space 304 that between first electrode material 300 and second electrode material 302, forms, then carry out processing procedure T
r
Refer again to Fig. 3 A and 3B, in some embodiments, before pouring into liquid precursor material 306 in the gap 304, apply first electrode material 300, and apply second electrode material 302 with second catalyst material 312 with first catalyst material 310.
In some embodiments, proton exchange membrane 308 comprises the material with equivalent weight, and wherein said equivalent weight is selected from less than about 1500 and greater than about 1000 equivalent weight, less than about 1000 and greater than about 800 equivalent weight, less than about 800 and greater than in about 500 equivalent weight and the 500 following equivalent weights.The conductivity by the representative PEM of fluent material preparation of the present invention that has different equivalent weights under the condition of complete aquation is provided among Fig. 4 to 8.
III.
Preparation comprises the method for the polymer dielectric of equivalent weight gradient
In addition, the synthetic method that can change liquid precursor material disclosed herein produces composition gradient, thus the performance of cutting character and improvement PEM of the present invention.Existing P EM typically comprises the material with single equivalent weight (EW), and this causes the problem of attending to one thing and lose sight of another between power density and methanol permeability.For instance, based on
High equivalent weight weight PEM methyl alcohol is not too permeated.But this material list reveals lower conductivity.The PEM of low equivalent weight provides higher conductance values with respect to the PEM of the high equivalent weight weight of material with comparable component, but allows high methanol permeability, and this can cause the violent reduction of power density.
The invention provides PEM with equivalent weight gradient.Under equivalent weight gradient disclosed herein, can all realize optimum performance in two fields (methanol permeability and conductivity).For example, use at anode to have more that the material of high equivalent weight weight provides low methanol permeability to PEM, be included in and have in the PEM the entire profile more that the material of low equivalent weight then provides higher power density.
With reference now to Fig. 9 A,, illustrates with multiple fluent material 902 preparation proton exchange membrane 900.In the present embodiment, multiple fluent material 902 comprises multiple fluent material 902a to 902f.In some embodiments, fluent material 902a to 902f comprises high glass-transition temperature (T
g)
The class material.But fluent material 902a to 902f is not limited to high T
gMaterial, and in some embodiments, fluent material 902a to 902f comprise fluoro or based on material or any material disclosed herein of Perfluoroelastomer.
In some embodiments, every kind of fluent material, for example 902a, 902b, 902c, 902d, 902e and 902f have different equivalent weights and (for example are respectively EW
a, EW
b, EW
c, EW
d, EW
eAnd EW
f(not shown)).Term used herein " equivalent weight " refers to comprise the weight of the acid material of monovalent acid functional group.Therefore, be that the equivalent of acidic-group of polymer dielectric is divided by the numerical value of polymer dielectric weight as the equivalent weight of polymer dielectric disclosed herein.In addition, term used herein " different equivalent weight " refers to and another equivalent weight (EW for example
b) differ the equivalent weight of about 50g/mol, for example EW
aFor example think that about 800 equivalent weight is different with about 750 equivalent weight.
Refer again to Fig. 9 A, compare with 902b to 902f, near the fluent material of anode 904, promptly a layer 902a has higher equivalent weight.In some embodiments, the equivalent weight of fluent material 902a to 902f has following trend: EW
aEW
bEW
cEW
dEW
eEW
f, wherein have minimum equivalent weight near the fluent material 902f of negative electrode 906.
In some embodiments, have one of at least among fluent material 902a, 902b, 902c, 902d, 902e and the 902f and be lower than 1500 equivalent weight.In some embodiments, have one of at least among fluent material 902a, 902b, 902c, 902d, 902e and the 902f and be lower than 1000 equivalent weight.In some embodiments, have one of at least among fluent material 902a, 902b, 902c, 902d, 902e and the 902f and be lower than 800 equivalent weight.In some embodiments, have one of at least among fluent material 902a, 902b, 902c, 902d, 902e and the 902f and be lower than 500 equivalent weight.The conductivity by the representative PEM of fluent material preparation of the present invention that has different equivalent weights under the condition of complete aquation is provided among Fig. 4 to 8.
With reference now to Fig. 9 B,, in some embodiments,, arrange the fluent material of high equivalent weight weight in order to reduce the methanol permeability of anode 904 PEM900 of place, for example have equivalent weight EW
a902a, for example use or be spun on the ground (for example anode 904), thereby on anode 904, form fluent material 902a layer, then use processing procedure T
rHandle, form the fluent material 908a that handles.The fluent material 908a that handles is with having equivalent weight EW
bThe fluent material than low equivalent weight (for example 902b) apply, handle forming the fluent material 908b (not shown) of handling then.Has equivalent weight gradient (EW for example according to formation
aTo EW
f) the needs of PEM 900 repeat this step.Therefore, in some embodiments, with the fluent material of negative electrode 906 immediate processing, for example the 908f (not shown) has minimum equivalent weight, for example EW
fTherefore, the inventive method can provide the reduction of methanol permeability and can promote proton to transmit the cross section by PEM 900 more easily at anode 904 places.
Therefore, in some embodiments, PEM 900 comprises the multiple layer polymer electrolyte, wherein the multiple layer polymer electrolyte comprises the ground floor of at least one first polymer dielectric, it contains the second layer of material with first equivalent weight and at least one second polymer dielectric, and it contains the material with second equivalent weight.In some embodiments, the multiple layer polymer electrolyte has the equivalent weight gradient.
Therefore, in some embodiments, the invention provides the method that preparation has the polymer dielectric of a plurality of equivalent weights, described method comprises:
(a) on ground, use first liquid precursor material with first equivalent weight;
(b) handle described first liquid precursor material, on ground, form the liquid precursor material that ground floor is handled;
(c) on the liquid precursor material that the ground floor on the ground is handled, use second liquid precursor material with second equivalent weight; And
(d) handle described second liquid precursor material, form polymer dielectric with a plurality of equivalent weights.
In some embodiments, first liquid precursor material and second liquid precursor material all are selected from the precursor and their combination of proton-conducting material, proton-conducting material.In some embodiments, first equivalent weight is greater than second equivalent weight.
In some embodiments, this ground is selected from anode and the negative electrode.In some embodiments, the processing of first liquid precursor material, second liquid precursor material and multiple liquid precursor material is selected from solidification process, chemical modification process, forms in process, solvent evaporation process and their combination of network.
In some embodiments, described method comprises with the predetermined multiple liquid precursor material repeating step (c) with a plurality of equivalent weights to (d), formation has the polymer dielectric of a plurality of equivalent weights, and wherein said multiple liquid precursor material is selected from the precursor and their combination of proton-conducting material, proton-conducting material.In some embodiments, second equivalent weight is greater than a plurality of equivalent weights.
Therefore, in some embodiments, the invention provides polymer dielectric with a plurality of equivalent weights by the inventive method preparation.In some embodiments, the invention provides the electrochemical cell that comprises polymer dielectric of the present invention with equivalent weight gradient.In some embodiments, described electrochemical cell is selected from fuel cell, chlor-alkali cell and the storage battery.
By measuring conductivity, power density, durability and particularly life-span, can estimate the performance of proton exchange membrane of the present invention.
IV.
The method for preparing membrane electrode assembly (MEA)
The present invention also provides the method for preparing membrane electrode assembly (MEA).In some embodiments, the method for preparing membrane electrode assembly comprises and uses liquid precursor material of the present invention to prepare accessible catalyst ink water composition.In addition, in some embodiments, the method for preparing membrane electrode assembly comprises by the inventive method to be provided proton exchange membrane, applies described proton exchange membrane with accessible catalyst ink water composition, thereby form the proton exchange membrane of coating, and in some embodiments, on the proton exchange membrane of described coating, use electrode material.
IV.A.
Prepare accessible catalyst ink method for compositions
In some embodiments, the invention describes the accessible catalyst ink method for compositions of preparation, described method comprises:
(a) provide liquid precursor material; And
(b), form accessible catalyst ink water composition with described liquid precursor material and catalyst mix.
In some embodiments, liquid precursor material comprises liquid PFPE material.In some embodiments, liquid PFPE material comprises end group, and wherein said end group is chemically stable after curing.In some embodiments, described chemically stable end group is selected from aryl end group and fluorinated ethylene ether end group.In some embodiments, described aryl end group comprises the styrene end group.
In some embodiments, described method further comprises liquid precursor material is mixed with monomer (for example vinyl monomer) and crosslinking agent.In some embodiments, vinyl monomer comprises proton conductive substance.In some embodiments, proton conductive substance is selected from the precursor of acid material and acid material.
In some embodiments, described accessible catalyst ink water composition comprises catalyst.In some embodiments, described catalyst comprises the metal that is selected from platinum, ruthenium, molybdenum, chromium and their combination.In some embodiments, described catalyst is selected from one of platinum catalyst and platinum alloy catalyst.In some embodiments, described accessible catalyst ink water composition comprises electrode material.In some embodiments, described electrode material comprises carbon black.
In some embodiments, described method comprises the accessible catalyst ink water composition of processing.In some embodiments, the processing of described accessible catalyst ink water composition is comprised be selected from solidification process, chemical modification process, form the processing procedure in process, solvent evaporation process and their combination of network.
Therefore, in some embodiments, the invention provides accessible catalyst ink water composition herein by the method preparation of describing.
IV.B.
Ground is used accessible catalyst ink method for compositions
In some embodiments, the invention provides ground is used accessible catalyst ink method for compositions.In some embodiments, described ground comprises electrode material.In some embodiments, described ground comprises proton exchange membrane.
With reference now to Figure 10 A,, in some embodiments, the accessible catalyst ink water composition 1000 of top firm description is administered on the electrode material 1002.In some embodiments, electrode material 1002 comprises carbon cloth.In some embodiments, electrode material 1002 comprises carbon paper.Subsequently by processing procedure T
rHandle accessible catalyst ink water composition 1000, thereby form catalyst belt (not shown), this just provides with the good of electrode material 1002 and has contacted.
With reference now to Figure 10 B,, in some embodiments, accessible catalyst ink water composition 1000 is administered on the proton exchange membrane 1004 of patterning.Subsequently by processing procedure T
rHandle accessible catalyst ink water composition 1000, thereby form catalyst belt (not shown), this just provides with the good of proton exchange membrane 1004 and has contacted.
Being used for one of coated electrode 1002 and proton exchange membrane 1004 or both methods can be selected from the method for the CVD, flame atomizing deposition, ink jet printing or the pulse laser desorption that strengthen including, but not limited to chemical vapor deposition (CVD), electron spray, electric field desorption, radio frequency plasma.In some embodiments, described method comprises the described accessible catalyst ink water composition of processing.In some embodiments, the processing of described accessible catalyst ink water composition comprises the processing procedure in process, solvent evaporation process and their combination that is selected from solidification process, chemical modification process, formation network.
In order to be used for different membrane electrode assemblies, can implement the method that the present invention describes independently.That is, in a membrane electrode assembly, the inventive method coated electrode material can be used, and in another membrane electrode assembly, the inventive method coating proton exchange membrane can be used.In addition, can use this two kinds of methods, for example the method for describing in Figure 10 A and Figure 10 B respectively prepares identical membrane electrode assembly.
IV.C.
The method of conformal spreading proton exchange membrane
In some embodiments, the invention provides with conformal spreading proton exchange membrane one of at least in accessible catalyst ink water composition and the electrode material.The coating that " conformal spreading " means for example accessible catalyst ink water composition and/or electrode material contacts with the feature structure conduction that for example comprises proton exchange membrane, thereby consistent with the geometry of its feature structure.
With reference now to Figure 11 A,, in some embodiments, with the PEM 1100 of accessible catalyst ink water composition 1102 conformal spreading patternings, then the electrode material 1104 with for example carbon black applies, thereby forms the planar surface 1106 of electrode material 1104.In some embodiments, then by processing procedure T
rHandle accessible catalyst ink water composition 1102.When randomly being arranged in the membrane electrode assembly (not shown), the plane coating of electrode material allows membrane electrode assembly to have flat surface at least on its one side.
With reference now to Figure 11 B,, in some embodiments, with the PEM 1100 of accessible catalyst ink water composition 1102 conformal spreading patternings, then with electrode material 1104 coatings, thus the conformal surface 1108 of formation electrode material 1104.In some embodiments, then by processing procedure T
rHandle accessible catalyst ink water composition 1102.
With reference now to Figure 11 C,, in some embodiments,, thereby forms the planar surface 1110 of accessible catalyst ink water composition 1102 with the PEM 1100 of accessible catalyst ink water composition 1102 conformal spreading patternings.Then apply with electrode material 1104, thus the conformal surface 1106 of formation electrode material 1104.In some embodiments, then by processing procedure T
rHandle accessible catalyst ink water composition 1102.When operationally placing the membrane electrode assembly (not shown), the plane coating of electrode material allows membrane electrode assembly to have flat surface at least on its one side.
Therefore, in some embodiments, described method comprise to proton exchange membrane and electrode material one of at least on conformally use accessible catalyst ink water composition.
For instance, in Figure 12 A and 12B, represented by using the scanning electron micrograph of electron spray deposition technique with the patterning PEM of catalyst conformal spreading.In addition, in Figure 13, represented by using the scanning electron micrograph of vapor deposition techniques with the patterning PEM of catalyst conformal spreading.The preparation of each has been described among the embodiment 8 among these PEM.
IV.D.
The method for preparing membrane electrode assembly (MEA)
The present invention also provides the method for preparing membrane electrode assembly.In some embodiments, the method for preparing membrane electrode assembly comprise preparation proton exchange membrane of the present invention, the accessible catalyst ink water composition of preparation, to ground use in accessible catalyst ink water composition and the conformal spreading proton exchange film method one of at least.
Therefore, in some embodiments, the method for described formation membrane electrode assembly comprises:
(a) provide proton exchange membrane, wherein said proton exchange membrane is from liquid precursor material preparation as described herein;
(b) provide first catalyst material and second catalyst material;
(c) provide first electrode material and second electrode material; And
(d) mode that is communicated with conduction is operationally settled described proton exchange membrane, described first and second catalyst materials and described first and second electrode materials, thereby forms membrane electrode assembly.
With reference now to Figure 14 A,, is provided for forming the embodiment of the inventive method of membrane electrode assembly.Continuing provides proton exchange membrane 1400 with reference to figure 14A.In some embodiments, proton exchange membrane 1400 comprises the 3 dimensional coil geometry shown in Figure 14 A.In some embodiments, first catalyst material 1402 contacts with proton exchange membrane 1400 conformals with second catalyst material 1404.First electrode material 1406 contacts with 1402 conformals of first catalyst material.Second electrode material 1408 contacts with 1404 conformals of second catalyst material.In some embodiments, first electrode material 1406 and second electrode material 1408 comprise plane geometric shape.In some embodiments, can pass through processing procedure T
rHandle each assembly of membrane electrode assembly, thereby excellent contact and mechanical stability are provided between each assembly.
Therefore, the invention provides and comprise the membrane electrode assembly that three-dimensional proton exchange membrane and bidimensional electrode and load conformally have catalyst.The three-dimensional proton exchange membrane that means for instance has the feature (feature) of stretching out from plane surface (for example referring to Figure 1B a plurality of architectural features 120).Bidimensional means electrode material for instance and comprises the plane surface that is communicated with proton exchange membrane conduction (for example referring to Figure 14 A first electrode material 1406 and second electrode material 1408).
With reference now to Figure 14 B,, provides proton exchange membrane 1400.In some embodiments, proton exchange membrane 1400 comprises 3 dimensional coil geometry as shown in Figure 14B, and wherein said 3 dimensional coil geometry comprises a plurality of depressions 1410.In some embodiments, first catalyst material 1412 and second catalyst material 1414 operationally are positioned at depression 1410.First electrode material 1406 contacts with 1412 conformals of first catalyst material.Second electrode material 1408 contacts with 1414 conformals of second catalyst material.In some embodiments, first electrode material 1406 and second electrode material 1408 comprise plane-bidimensional geometry.In some embodiments, can pass through processing procedure T
rHandle each assembly of membrane electrode assembly, thereby excellent contact and mechanical stability are provided between each assembly.Therefore, the invention provides that to comprise three-dimensional proton exchange membrane and bidimensional electrode be not the membrane electrode assembly of supported catalyst conformally.
With reference now to Figure 15,, provides proton exchange membrane 1500.In some embodiments, proton exchange membrane 1500 comprises the 3 dimensional coil geometry with a plurality of depressions 1502.In some embodiments, first catalyst material 1504 contacts with proton exchange membrane 1500 conformals with second catalyst material 1506.In some embodiments, first electrode material 1508 is positioned at depression 1502 and operationally contacts with first catalyst material 1504.In some embodiments, second electrode material 1510 is positioned at depression 1502 and operationally contacts with catalyst material 1506.In some embodiments, can pass through processing procedure T
rHandle each assembly of membrane electrode assembly, thereby excellent contact and mechanical stability are provided between each assembly.Therefore, the invention provides and comprise the membrane electrode assembly that three-dimensional proton exchange membrane and three-diemsnional electrode and load conformally have catalyst.
In some embodiments, form proton exchange membrane by method described herein, for example 1400 of Figure 14 A and 14B and Figure 15 1500.In some embodiments,, for example operationally arrange liquid precursor material between first electrode material 1508 of Figure 15 and second electrode material 1510, handle this liquid precursor material then and form proton exchange membrane by at two electrode materials.
Therefore, in some embodiments, the invention provides the method for preparing membrane electrode assembly, described method comprises:
(a) provide first electrode material;
(b) provide second electrode material;
(c) settle described first electrode material and second electrode material in the steric mode that between described first electrode material and second electrode material, forms spacing;
(d) arrange liquid precursor material in the spacing between described first electrode material and second electrode material; And
(e) handle described liquid precursor material, form membrane electrode assembly.
In some embodiments, described liquid precursor material is selected from the precursor of proton-conducting material, proton-conducting material and their combination.
In some embodiments, described method comprises:
(a) described first electrode material is contacted with first catalyst material;
(b) described second electrode material is contacted with second catalyst material; And
(c) so that described first catalyst material and second catalyst material face with each other and the spatial placement mode that forms spacing between described first catalyst material and second catalyst material is settled described first electrode material and second electrode material.
In addition, in some embodiments, first catalyst material and second catalyst material comprise one of at least accessible catalyst ink water composition.In some embodiments, described method further comprises use described accessible catalyst ink water composition on proton exchange membrane.In some embodiments, described method comprise in first and second electrode materials one of at least on use described accessible catalyst ink water composition.In some embodiments, described method comprise in the proton exchange membrane and first and second electrode materials one of at least on use described accessible catalyst ink water composition.
In some embodiments, use described accessible catalyst ink water composition by the method that is selected from CVD method, flame atomizing deposition process, ink jet printing method or the pulse laser desorption method that strengthens including, but not limited to chemical vapor deposition (CVD) method, method of electrospraying, electric field desorption method, radio frequency plasma.
In some embodiments, described electrode material is selected from carbon cloth, carbon paper and carbon black.In some embodiments, described electrode material comprises the electrode material of patterning.
Therefore, in some embodiments, the invention provides membrane electrode assembly (MEA) by method preparation as herein described.
In some embodiments, handle electrode material, for example carbon cloth, carbon paper and/or carbon black increase its surface area, thereby increase the power density that wherein operationally is furnished with the electrochemical cell of described electrode material.With reference now to Figure 16,, provides electrode material 1600.Can use traditional photoetching technique (not shown) patterned electrodes material 1600, form the electrode material 1602 of patterning, perhaps directly use electron beam, for example the etchant EA of Figure 16 comes patterning.In some embodiments, electrode material 1600 may further include the photoresist 1604 that for example is used for electron beam lithography.In some embodiments, can provide the mask 1606 that for example is used for plasma etching (for example oxygen reactive ion etching).
Therefore, in some embodiments, by being selected from the process patterned electrodes material in the following process:
(a) photoetching process;
(b) electron-beam direct writing process (direct electon beam process);
(c) make with photoresist electron beam lithography process (electron beam lithographyprocess); And
(d) plasma etch process of use mask.
In some embodiments, described method for etching plasma comprises oxygen reactive ion etching method.
V.
Form the method for electrochemical cell
In some embodiments, the invention provides and form for example method of the electrochemical cell of fuel cell.With reference now to Figure 17 A,, provides proton exchange membrane 1700.Can prepare proton exchange membrane 1700 from liquid precursor material of the present invention by method as herein described.Operationally place proton exchange membrane 1700 between first catalyst material 1702 and second catalyst material 1704 and contact with it.In some embodiments, first catalyst material 1702 and second catalyst material 1704 comprise the metal that is selected from platinum, ruthenium, molybdenum, chromium and their combination independently of one another.
Continue with reference to figure 17A, first catalyst material 1702 operationally contacts with first electrode material 1706.In some embodiments, first electrode material 1706 comprises first surface 1706a and second surface 1706b.Therefore, in some embodiments, first surface 1706a and second surface 1706b operationally contact with first catalyst material 1702 one of at least.In some embodiments, one of at least with first catalyst material 1702 coating first surface 1706a and second surface 1706b.In some embodiments, one of at least with first catalyst material 1702 dipping first surface 1706a and second surface 1706b.
Continue with reference to figure 17A, second catalyst material 1704 operationally contacts with second electrode material 1708.In some embodiments, second electrode material 1708 has first surface 1708a and second surface 1708b.Therefore, in some embodiments, first surface 1708a and second surface 1708b operationally contact with second catalyst material 1704 one of at least.In some embodiments, one of at least with second catalyst material 1704 coating first surface 1708a and second surface 1708b.In some embodiments, one of at least with second catalyst material 1704 dipping first surface 1708a and second surface 1708b.
Continue with reference to figure 17A, so by operationally settling proton exchange membrane 1700, first catalyst layer 1702, first electrode material 1706, second catalyst layer 1704 and second electrode material 1708 to form membrane electrode assembly 1710.Can in the electrochemical cell of for example fuel cell, operationally settle membrane electrode assembly 1710.
Continue with reference to figure 17A, first outer 1712 and second skin 1714 is provided.In some embodiments, first outer 1712 and second skin 1714 is made up of PFPE as described herein (PFPE) material.First skin 1712 can further comprise a plurality of fluid channel 1716, can introduce fuel F by this fluid channel
1, second skin 1714 can further comprise a plurality of fluid channel 1718, can introduce fuel F by this fluid channel
2
In some embodiments, first electrode material 1706 comprise anode and with fuel F
1Fluid is communicated with, and it comprises anode fuel in some embodiments.In some embodiments, described anode fuel (fuel F for example
1) be selected from H
2, alkane, alkylol, dialkyl ether and glycol.In some embodiments, described alkane is selected from methane, ethane, propane and butane.In some embodiments, described alkylol is selected from methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol and hexanol.In some embodiments, described alkylol comprises methyl alcohol.In some embodiments, described dialkyl ether comprises dimethyl ether.In some embodiments, described glycol comprises ethylene glycol.
In some embodiments, second electrode material 1708 comprise negative electrode and with fuel F
2Fluid is communicated with, and it comprises negative electrode fuel in some embodiments.In some embodiments, described negative electrode fuel (fuel F for example
2) comprise and comprise oxygen (O
2) gas, for example air.In some embodiments, described negative electrode fuel comprises air/water mixture.
In some embodiments, described electrochemical cell comprises that at least one electricity output connects E
0
With reference now to Figure 17 B,, in some embodiments, described a plurality of fluid channel 1716 comprise at least one inlet 1720.In some embodiments, inlet 1720 and fuels sources 1722 fluid connections.In some embodiments, fuels sources 1722 comprises fuel F
1In some embodiments, fuel F
1Be selected from anode fuel and negative electrode fuel.
Continue with reference to figure 17B, in some embodiments, described a plurality of fluid channel 1718 comprise at least one inlet 1724.In some embodiments, inlet 1724 and fuels sources 1726 fluid connections.In some embodiments, fuels sources 1726 comprises fuel F
2In some embodiments, fuel F
2Be selected from anode fuel and negative electrode fuel.
In some embodiments, described a plurality of fluid channel 1716 comprises at least one outlet 1728.In some embodiments, outlet 1728 and fuel recycle passage 1730 fluid connections.In some embodiments, outlet 1728 and refuse outlet (waste exhaustport) 1732 fluid connections.
In some embodiments, described a plurality of fluid channel 1718 comprises outlet 1734.In some embodiments, outlet 1734 and fuel recycle passage 1736 fluid connections.In some embodiments, outlet 1734 and refuse outlet 1738 fluid connections.
In some embodiments, described a plurality of fluid channel 1716 comprise a plurality of valves, for example 1740a, 1740b and 1740c.In some embodiments, a plurality of valve 1740a, 1740b and 1740c comprise the pressure operable valve (not shown).In some embodiments, described a plurality of fluid channel 1718 comprise a plurality of valves, for example 1742a, 1742b and 1742c.In some embodiments, a plurality of valve 1742a, 1742b and 1742c comprise the pressure operable valve (not shown).
In some embodiments, described a plurality of fluid channel 1716 and a plurality of fluid channel 1718 each comprise fluid channel network (not shown).
In some embodiments, prepare microfluidic device by the soft lithographic method.Term used herein " soft lithographic " refers to by using the elastomer seal that micron and nanoscale features (feature) are transferred to method on the ground.Soft lithographic occurs as the alternative of conventional lithography method, makes the characteristic size less than about 100 nanometers.Several method contained in term used herein " soft lithographic ", includes but not limited to little molding (SAMIM) that imprint lithography (IL), duplicating molded, micro-contact printing (MCP), the little molding of capillary (MIMIC) and solvent are auxiliary.
With reference now to Figure 18 A-18C,, these figure have represented to be used for forming the schematic diagram of the inventive method embodiment of PFPE (PFPE) layer that comprises a plurality of fluid channel.Ground 1800 with the patterned surface 1802 that comprises projection (raised protrusion) 1804 has been described.Therefore, the patterned surface 1802 of ground 1800 comprises the projection 1804 that at least one forms pattern form.In some embodiments, the patterned surface 1802 of ground 1800 comprises the projection 1804 of a plurality of formation complex patterns.
Find out preferably that from Figure 18 B polymer precursor 1806 is placed on the patterned surface 1802 of ground 1800.Polymer precursor 1806 can comprise PFPE.Shown in Figure 18 B, by processing procedure T
r, for example handle polymer precursor 1806, thereby form the PFPE patterned layer 1808 of the photocuring shown in Figure 18 C with UV-irradiation.
Shown in Figure 18 C, the PFPE patterned layer 1808 of photocuring is included in the depression 1810 that patterned layer 1808 bottoms form.The size of the projection 1804 of the size of depression 1810 and the patterned surface 1802 of ground 1800 is corresponding.In some embodiments, depression 1810 comprises at least one passage 1812, and it comprises the micron order passage in some embodiments of the present invention.From the patterned surface 1802 of ground 1800, remove patterned layer 1808, produce microfluidic device 1814.Therefore, in some embodiments, the soft lithographic method comprises makes liquid precursor material contact with the ground (for example silicon chip) of patterning.In some embodiments, described method further comprises handles described liquid precursor material, forms crosslinked polymer.In some embodiments, described processing procedure is selected from solidification process, chemical modification process, the process that forms network and their combination.
In some embodiments, described method further comprises removes crosslinked polymer from ground, thereby produces " seal " of required pattern.
In this microfluidic device, typically use poly-(dimethyl siloxane) (PDMS) elastomeric material.But owing to destroy micrometer-class, the swelling of PDMS material makes it receive restriction in direct methanol fuel cell and the application in the fuel cell that comprises other organic liquid.In addition, the PDMS material is typically also to the bronsted lowry acids and bases bronsted lowry instability.
The present invention by the PFPE material that uses photocuring all or part of solved above-mentioned about the elastomeric problem of PDMS.In some embodiments, the PFPE material comprises fluoro, functionalized PFPE material, the durable elastic body that it has liquid viscosity in some embodiments and can be cured into the chemical resistance that shows typical fluoropolymer.
Therefore, in some embodiments, the present invention includes the PFPE sill of curing.In some embodiments, curing comprises the radically curing method.In some embodiments, the radically curing method further comprises other monomer of interpolation and macromonomer in the PFPE resin.Can regulate physical property by other monomer of interpolation and macromonomer in the PFPE resin, including, but not limited to modulus, bending strength, wetting characteristics, permeability, adhesiveness and reactivity.
VI.
The method of operation electrochemical cell
The present invention also provides the method for the electrochemical cell of operational example such as fuel cell.In some embodiments, described method comprises:
(a) provide and comprise the electrochemical cell of one deck PFPE (PFPE) material at least, described PFPE material comprises at least one fluid channel;
(b) the first electrode reaction thing and the second electrode reaction thing are assigned in the electrochemical cell; And
(c) from described electrochemical cell, produce electricity output.
In some embodiments, the proton exchange membrane of electrochemical cell comprises from the polymer dielectric of the preparation of liquid precursor material as described herein.
In some embodiments, the described first electrode reaction thing is selected from H
2, alkane, alkylol, dialkyl ether and glycol.In some embodiments, described alkane is selected from methane, ethane, propane and butane.In some embodiments, described alkylol is selected from methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol and hexanol.In some embodiments, described alkylol comprises methyl alcohol.In some embodiments, described dialkyl ether comprises dimethyl ether.In some embodiments, described glycol comprises ethylene glycol.In some embodiments, the described second electrode reaction thing comprises and contains oxygen (O
2) gas, air for example, and in some embodiments, comprise air/water mixture.
In some embodiments, described method comprises the electricity output that extraction is produced by described electrochemical cell.In some embodiments, described electricity output is in from about 100 milliwatts to about 20 watts scope.
In some embodiments, the method for operation electrochemical cell further comprises to supply of equipment electric power.In some embodiments, described equipment comprises static device (stationarydevice).In some embodiments, described static device comprises generator.In some embodiments, described equipment comprises portable set.In some embodiments, described portable set is selected from portable electric generator, portable instrument, electric tool, electronic equipment, road or traffic sign, stand-by power supply and individual vehicle.In some embodiments, described electronic equipment is selected from consumer-elcetronics devices and Military Electronic Equipment.In some embodiments, described equipment comprises automobile equipment.
Embodiment
In order to instruct persons skilled in the art to implement representative embodiment of the present invention, the following examples have been provided.From the general technology level of the disclosure of invention and this area, the technical staff is appreciated that the following examples are exemplary and can use a large amount of variations, modification and change, and can not deviate from scope of the present invention.
Synthesizing of crosslinkable PFPE liquid precursor
Embodiment 1.1 has the synthetic of crosslinkable PFPE liquid precursor that styrene connects
To poly-(tetrafluoroethene-copolymerization-difluoro oxirane) α, two end of the chains of ω glycol (ZDOL) (PFPE, the average about 3800 gram/moles of Mn) add styrene and connect by interfacial reaction.In typical synthesizing, in round-bottomed flask, add PFPE (20 grams, 5.26 mMs), solcane (10 milliliters) and hydrogen sulfate TBuA (1.0 grams, 2.95 mMs).Dissolving KOH in deionized water (20 milliliters) (10 grams, 0.18 mole) adds this KOH aqueous solution in the round-bottomed flask then.After adding 4-vinyl chloride (2 milliliters, 2.8 mMs), 45 ℃ of following vigorous stirring reactant mixtures 48 hours.Make product pass through 0.22 micron filter, remove the brown solid of gained.Then, extract solution three times and, remove any impurity with deionized water with carbon black stirring 1 hour.Make the filter of mixture by 0.22 micron removing carbon black, and vacuumize at room temperature, remove and desolvate.Products therefrom (S-PFPE) is limpid thick liquid.
Synthetic and the photocuring of embodiment 1.2 functional PFPE
Synthetic and the photocuring of route 1. functional PFPE
Embodiment 1.3. representative perfluor polyethers
PFPE of the present invention is including, but not limited to comprising the PFPE material of following skeleton structure:
Embodiment 2
Synthesizing of cross-linking system
Embodiment 2.1. totally considers
Strong acid and polyfunctional monomer can radical polymerizations or by different chemism polymerizations.Polyfunctional monomer can be strong acid or can have at least two degrees of functionality.The example of strong acid that can be used for the cross-linking system of these electrochemical cell application is perfluor-2-(2-fluorine nyl ethoxy) propyl vinyl ether (PSEPVE).Other can be imido sulphonyl-based compound as the super acid of strong acid or polyfunctional monomer.
In the round-bottomed flask under the argon gas, mix described strong acid and polyfunctional monomer, use fluoro or perfluoro solvent as required.The ratio of two components changes according to required crosslink density and equivalent weight.Can and whether mix easily according to concrete component and change reaction condition, for example temperature and reaction time.
The liquid precursor that will comprise reactant mixture pours on the ground of sheet glass or patterning (for example mould).The steel keeper control thickness of use standard.By using UV-irradiation chemical crosslinking liquid precursor or heat cross-linking liquid precursor under nitrogen wash.The mechanism of chemical crosslinking depends on used initator.In case prepare crosslinked network, use the hydrolysis of alkali and acid that any residual conduction sites (conducting site) is changed into acid, be used to increase proton conduction.
Embodiment 2.2. is the polyfunctional monomer of fluoro divinyl ether for example
The bifunctional monomer of non-conduction produces the stable proton conduction network of mechanics when reacting with strong acid.Degree of functionality is more than or equal to 2 commercially available compound, for example the strong acid reaction of 4,4 '-two (4-trifluoro-ethylene oxygen) biphenyl (compound 1) and for example PSEPVE.At the liquid precursor state, reactant mixture presents the shape of surface/mould, and radical polymerization when adding initator, heat or photochemical polymerization in inert atmosphere.
Embodiment 2.3. is the polyfunctional monomer of three (trifluoro-ethylene) benzene for example
If mechanism of crosslinking is feasible, liquid precursor is a patternable.When solidifying with strong acid, the radically curing of trifunctional monomer provides the network of the chemical crosslinking that can be used for proton conduction.The example of trifunctional monomer is three (α, β, a β-trifluoro-ethylene) benzene (compound 2), and it uses 1,3,5-tribromo-benzene (referring to route 2) preparation.Raw material in the route 2 also can be represented to be used for subsequently and the crosslinked trifunctional monomer of strong acid.The example of strong acid is PSEPVE.Can be according to the mode described in the embodiment 2.2, the crosslinked reactant mixture that is in the liquid precursor state.
Compound 2. trifluoro-ethylene benzene
Embodiment 2.4. is the polyfunctional monomer of fluoro divinyl ether imido sulphonyl for example
Difunctional macromonomer (also being super acid) reacts with another kind of strong acid (for example PSEPVE), obtains the mechanics stable network of high conductance.In the liquid precursor form, this reactant presents the shape of any mould before crosslinked.Crosslinked generation high surface subsequently, the film of high conductance.The example that is used as the super acid of difunctional macromonomer is two (PSEPVE-yl) imido sulphonyl (compound 3), and it prepares by imido sulphonyl chemistry (referring to route 3 and 4).Reactant mixture can solidify under the condition described in the embodiment 2.2.
Compound 3. fluoro divinyl imido sulphonyl
Embodiment 2.5. is the polyfunctional monomer of fluoro divinyl ether two imido sulphonyl for example
Use for example strong acid and the disulfonyl fluorine of PSEPVE, use imido sulphonyl chemical preparation divinyl ether two imido sulphonyl, to obtain this crosslinkable super acid monomer (compound 4, route 6).The disulfonyl fluorine can use diiodo-alkane (for example alpha, omega diiodo perfluo-alkane) to prepare (route 5).Divinyl ether two imido sulphonyl and another kind of strong acid (for example PSEPVE) reaction, the film of formation high conductance.Reactant can solidify under the condition described in the embodiment 2.2.
Compound 4. fluoro divinyl ethers two imido sulphonyl
Route 2. tribromo-benzenes change into three (α, β, β-trifluoro-ethylene) benzene (referring to
DesMarteau, etc.,Chem.Commun., 2596-2597 (2003)).
The preparation of route 3.PSEPVE-base silane sulfimide (
Referring to DesMarteau, D.D., Deng,Journal of Fluorine Chemistry, 125,1231-1240 (2004)).
The preparation of route 4.PSEPVE-base imido sulphonyl.
The preparation of route 5. disulfonyl fluorine (
Referring toDesMarteau
, D.D., etc.,Journal ofFluorine Chemistry, 125,1179-1185 (2004)).
The preparation of route 6. divinyl ethers two imido sulphonyl.
Embodiment 3
Synthesizing of crosslinkable terpolymer
Embodiment 3.1. totally considers
Polymerization comprises the terpolymer of Fluorine containing olefine, strong acid and low-molecular-weight cure site monomer (CSM).The example of Fluorine containing olefine is tetrafluoroethene (TFE), and as strong acid, selects perfluor-2-(2-fluorine nyl ethoxy) propyl vinyl ether (PSEPVE).Typical polymerization can be loaded with 40% solid.The solvent that polymerization is selected for the TFE base randomly is carbon dioxide (CO
2).Initiator concentration is regulated required molecular weight.Initiator concentration is high more will to cause low more relative molecular weight, will cause high more relative molecular weight and initiator concentration is low more, carry out radical polymerization under thermal initiator.Reaction time becomes according to required conversion.Preferably use solid site monomer commonly used in fluoroelastomer and Perfluoroelastomer technology to carry out polymerization.For instance, described solid site monomer can comprise cyano group vinethene, brominated monomer, brominated alkene, brominated vinethene, contain the iodine monomer, contain iodine alkene, contain iodoethylene ether, have itrile group Fluorine containing olefine, have an itrile group contain fluroxene, 1,1,3,3,3-five fluorine propylene, perfluor (2-benzene oxygen propyl group) vinethene and unconjugated diene.
After the polymerization and before the terpolymer hydrolysis, can the crosslinked terpolymer that forms by the polymerization of Fluorine containing olefine, strong acid and cure site monomer (CSM).Described polymerizate comprises that Mooney viscosity is less than or equal to 160 natural gum or liquid.In inert atmosphere, pour into terpolymer in the mould with required pattern or on the sheet glass.Thickness between the steel keeper control sheet glass of use standard.Terpolymer presents the shape of the mould of patterning.Randomly be cured chemistry according to fluoroelastomer and Perfluoroelastomer technology.By various cure systems (comprising heat or γ radiation) the described liquid precursor of chemical crosslinking.According to CSM, also can flood peroxide-based or bis-phenol cure system.Produce the film of the active surface area chemical crosslinking higher than the geometrical surface of mould.Produce the proton-conductive films of patterning subsequently with high mechanical integrity by hydrolysis (with alkali and acid).
Embodiment 3.2. has the terpolymer of brominated cure site monomer
For the polymerization of the terpolymer that comprises Fluorine containing olefine, strong acid and cure site monomer, select brominated cure site monomer.Bromine-containing compound as cure site monomer can comprise ethene bromine, 1-bromo-2,2-difluoroethylene, perfluor allyl bromide, bromoallylene, 4-bromo-1,1,2-trifluoro butylene, 4-bromine perfluor-1-butylene, 4-bromo-3,3,4,4-tetrafluoro-1-butylene, bromotrifluoethylene and perfluor bromo-vinethene.
Embodiment 3.3. has the terpolymer of the cure site monomer that comprises the cyano group vinethene
For the polymerization of the terpolymer that comprises Fluorine containing olefine, strong acid and cure site monomer, select the cure site monomer of cyano-containing vinethene.The compound that is used as the cyano-containing vinethene of cure site monomer can comprise perfluor (8-cyano group-5-methyl-3,6-dioxy (dioca)-1-octene) and perfluor (9-cyano group-5-methyl-3,6-dioxy-1-octene).
Embodiment 4
The preparation of other fluent material
Embodiment 4.1. is at CO
2In synthetic
Route 7. is at CO
2In synthetic
Embodiment 4.2.'s poly-(TFE-Nb-PSEPVE) is synthetic
Synthesizing of route 8. poly-(TFE-Nb-PSEPVE)
Embodiment 4.3.'s poly-(TFE-PDD-PSEPVE) is synthetic
Synthesizing of route 9. poly-(TFE-PDD-PSEPVE)
Synthesizing of embodiment 4.4. norbornene derivative
Synthesizing of route 10. norbornene derivatives
Embodiment 4.5. contains the PEM of vinyl alcohol
Route 11. contains the PEM of vinyl alcohol
Embodiment 5
Synthesizing of proton-conducting material precursor
Synthesizing of embodiment 5.1. styrene sulfonate
Flow down adding 4-Ethenylbenzene sulfonic acid chloride (37.5 mM), 3,3,4,4,5,5,6,6,7,7,8,8 in round-bottomed flask, 8-13 fluoro-1-octanols (37.5 mM), triethylamine (10 milliliters) and pyridine (20 milliliters) at Ar.At room temperature stir gained slurry 20 hours (h).Then reactant mixture is poured into cancellation triethylamine in excessive hydrochloric acid-ice bath.With the extracted by ether aqueous solution three times, and water, 10% NaOH solution and 10% NaCl solution wash the ether layer of merging in proper order.Then at MgSO
4Went up dry ethereal solution 1 hour.After leaching MgSO
4And remove ether by vacuum evaporation.The gained styrene sulfonate is the about 40 ℃ yellow solid of fusing point.
Synthesizing of embodiment 5.2. styrene sulfonate
Flow down adding 4-Ethenylbenzene sulfonic acid chloride (37.5 mM), 2,2,3,3,4,4,5,5,6,6,7,7 in round-bottomed flask, 7-13 fluoro-1-enanthol (37.5 mM), triethylamine (10 milliliters) and pyridine (20 milliliters) at Ar.At room temperature stir gained slurry 20h.Then reactant mixture is poured into cancellation triethylamine in excessive hydrochloric acid-ice bath.With the extracted by ether aqueous solution three times, and water, 10% NaOH solution and 10% NaCl solution wash the ether layer of merging in proper order.Then at MgSO
4Went up dry ethereal solution 1 hour.After leaching MgSO
4And remove ether by vacuum evaporation.
Embodiment 6
The preparation of proton exchange membrane
The preparation of the proton exchange membrane of embodiment 6.1.EW1900
At room temperature mix 70 weight %S-PFPE and 30 weight % styrene sulfonate.Be heated to mixture more than 40 ℃ and become uniform yellow liquid.This liquid precursor is poured on the pre-warmed sheet glass.Steel keeper (spacer) the control thickness of use standard.Under nitrogen wash, came the described liquid precursor of chemical crosslinking in 10 minutes with ultraviolet light (λ=365 nanometers) irradiation.The film of gained is the form of ester, and is transparent and slightly yellow.
For sulfonate ester group is changed into sulfonic acid, this film is immersed in the mixture of the aqueous solution of 30%NaOH and methyl alcohol (5:6 volume) and spend the night, refluxed then 10 hours.Use the water rinse film then and in 24 hours, use the HCl solution of 20 weight % of new system to stir 4 times.The film of gained is the form of acid.The HCl that the water flush away is residual.The PEM that makes has the equivalent of 1900 gram/moles.By the conductibility of the PEM under the complete aquation condition of AC impedance measurement, the result as shown in Figure 4.
The preparation of the proton exchange membrane of embodiment 6.2.EW1250
At room temperature mix 60 weight %S-PFPE and 40 weight % styrene sulfonate.Be heated to mixture more than 40 ℃ and become uniform yellow liquid.This liquid precursor is poured on the pre-warmed sheet glass.The steel keeper control thickness of use standard.Under nitrogen wash, came the described liquid precursor of chemical crosslinking in 10 minutes with ultraviolet light (λ=365 nanometers) irradiation.The film of gained is the form of ester, and is transparent and slightly yellow.
For sulfonate ester group is changed into sulfonic acid, this film is immersed in the mixture of the aqueous solution of 30% NaOH and methyl alcohol (5:6 volume) and spend the night, refluxed then 10 hours.Use the water rinse film then and in 24 hours, use the HCl solution of 20 weight % of new system to stir 4 times.The film of gained is the form of acid.The HCl that the water flush away is residual.The PEM that makes has the equivalent of 1250 gram/moles.By the conductibility of the PEM under the complete aquation condition of AC impedance measurement, the result as shown in Figure 5.
The preparation of the proton exchange membrane of embodiment 6.3.EW850
At room temperature mix 50 weight %S-PFPE and 50 weight % styrene sulfonate.Be heated to mixture more than 40 ℃ and become uniform yellow liquid.This liquid precursor is poured on the pre-warmed sheet glass.The steel keeper control thickness of use standard.Under nitrogen wash, came the described liquid precursor of chemical crosslinking in 10 minutes with ultraviolet light (λ=365 nanometers) irradiation.The film of gained is the form of ester, and is transparent and slightly yellow.
For sulfonate ester group is changed into sulfonic acid, this film is immersed in the mixture of the aqueous solution of 30% NaOH and methyl alcohol (5:6 volume) and spend the night, refluxed then 10 hours.Use the water rinse film then and in 24 hours, use the HCl solution of 20 weight % of new system to stir 4 times.The film of gained is the form of acid.The HCl that the water flush away is residual.The PEM that makes has the equivalent of 850 gram/moles.By the conductibility of the PEM under the complete aquation condition of AC impedance measurement, the result as shown in Figure 6.
The preparation of the proton exchange membrane of embodiment 6.4.EW660
At room temperature mix 40 weight %S-PFPE and 60 weight % styrene sulfonate.Be heated to mixture more than 40 ℃ and become uniform yellow liquid.This liquid precursor is poured on the pre-warmed sheet glass.The steel keeper control thickness of use standard.Under nitrogen wash, came the described liquid precursor of chemical crosslinking in 10 minutes with ultraviolet light (λ=365 nanometers) irradiation.The film of gained is the form of ester, and is transparent and slightly yellow.
For sulfonate ester group is changed into sulfonic acid, this film is immersed in the mixture of the aqueous solution of 30% NaOH and methyl alcohol (5:6 volume) and spend the night, refluxed then 10 hours.Use the water rinse film then and in 24 hours, use the HCl solution of 20 weight % of new system to stir 4 times.The film of gained is the form of acid.The HCl that the water flush away is residual.The PEM that makes has the equivalent of 660 gram/moles.By the conductibility of the PEM under the complete aquation condition of AC impedance measurement, the result as shown in Figure 7.
The preparation of the proton exchange membrane of embodiment 6.5.EW550
At room temperature mix 30 weight %S-PFPE and 70 weight % styrene sulfonate.Be heated to mixture more than 40 ℃ and become uniform yellow liquid.This liquid precursor is poured on the pre-warmed sheet glass.The steel keeper control thickness of use standard.Under nitrogen wash, came the described liquid precursor of chemical crosslinking in 10 minutes with ultraviolet light (λ=365 nanometers) irradiation.The film of gained is the form of ester, and is transparent and slightly yellow.
For sulfonate ester group is changed into sulfonic acid, this film is immersed in the mixture of the aqueous solution of 30% NaOH and methyl alcohol (5:6 volume) and spend the night, refluxed then 10 hours.Use the water rinse film then and in 24 hours, use the HCl solution of 20 weight % of new system to stir 4 times.The film of gained is the form of acid.The HCl that the water flush away is residual.The PEM that makes has the equivalent of 550 gram/moles.By the conductibility of the PEM under the complete aquation condition of AC impedance measurement, the result as shown in Figure 8.
Embodiment 7
Make the PEM of high surface by soft lithography
Manufacturing with PEM of sharkskin pattern
According to required mixed S-PFPE and styrene sulfonate.Be heated to mixture more than 40 ℃ and become uniform yellow liquid.This liquid precursor is poured on the pre-warmed silicon chip with sharkskin pattern.The steel keeper control thickness of use standard.Under nitrogen wash, came the described liquid precursor of chemical crosslinking in 10 minutes with ultraviolet light (λ=365 nanometers) irradiation.After curing, take off the film of patterning from silicon chip.The film of gained is the form of ester, and is transparent and slightly yellow.
For sulfonate ester group is changed into sulfonic acid, this film is immersed in the mixture of the aqueous solution of 30% NaOH and methyl alcohol (5:6 volume) and spend the night, refluxed then 10 hours.Use the water rinse film then and in 24 hours, use the HCl solution of 20 weight % of new system to stir 4 times.The film of gained is the form of acid.The HCl that the water flush away is residual.
Before the hydrolysis and the scanning electron micrograph of the PEM after the hydrolysis with sharkskin pattern as shown in Figure 2A and 2B.The characteristic size of sharkskin pattern is 2 microns wide and 8 microns high.By using described sharkskin pattern, the surface area of the PEM of patterning is bigger five times than corresponding flat PEM approximately.As shown in the figure, easily obtained the pattern of high-fidelity by the soft lithographic approach.After hydrolysis,, still kept original feature because the suction pattern expands.
Embodiment 8
Conformal application of catalyst on PEM
Embodiment 8.1. is by electron spray technology deposited catalyst on PEM
Go up the catalyst that deposition comprises platinum or is dispersed in the platinum on the carbon by the electron spray technology to three-dimensional PEM with sharkskin pattern.Figure 12 A and 12B represent to deposit the scanning electron micrograph of the PEM of catalyst.
Embodiment 8.2. is by vapor deposition techniques deposited catalyst on PEM
Go up the deposition platinum catalyst by vapor deposition techniques to three-dimensional PEM with sharkskin pattern.Figure 13 represents to deposit the scanning electron micrograph of the PEM of catalyst.
Embodiment 9
The preparation of three-dimensional MEA
Embodiment 9.1.
The liquid precursor approach also provides three-dimensional films electrode assemblie (MEA) and fuel battery.Figure 14 A and 14B have shown the schematic diagram that the MEA structure of catalyst is arranged based on three-dimensional films and bidimensional electrode and conformal or non-load conformally.
Embodiment 9.2.
The liquid precursor approach also provides three-dimensional (3-D) membrane electrode assembly (MEA) and fuel battery.Figure 15 has shown the schematic diagram that the MEA structure of catalyst is arranged based on three-dimensional films and three-diemsnional electrode and load conformally.
Be to be understood that to change many details of the present invention, and can not deviate from scope of the present invention.In addition, above stated specification is not to be used to limit the present invention just for illustrating.
Claims (64)
1. the method for preparing polymer dielectric, described method comprises:
(a) provide 100% liquid precursor material of solidifying, wherein said 100% liquid precursor material of solidifying comprises the polymerizable material of about 70 weight % to about 100 weight %; And
(b) handle described 100% liquid precursor material of solidifying, form polymer dielectric.
2. the process of claim 1 wherein that described 100% liquid precursor material of solidifying comprises the precursor that is selected from proton-conducting material, proton-conducting material and the material in their combination.
3. the process of claim 1 wherein that described 100% liquid precursor material of solidifying comprises the material that is selected from monomer, oligomer, macromonomer, ionomer and their combination.
4. the method for claim 3 comprises one of at least functionalized PFPE (PFPE) material in wherein said monomer, oligomer, macromonomer and the ionomer.
5. the method for claim 4, wherein said functionalized PFPE (PFPE) material comprises the skeleton structure that is selected from the following structure:
With
Wherein exist or do not have X, and when having X, comprise end-capping group, and n is the integer of 1-100.
6. the method for claim 5, wherein said functionalized PFPE material is selected from the following material:
With
Wherein R is selected from alkyl, substituted alkyl, aryl and substituted aryl, and wherein m and n each be the integer of 1-100 independently of one another.
7. the method for claim 3, wherein said ionomer is selected from the derivative and phosphoric acid material of sulfonic acid material, sulfonic acid material.
8. the method for claim 7, the derivative of wherein said sulfonic acid material comprise and are selected from following material:
Wherein:
Y is selected from-SO
2F and-SO
3H;
R
1Be selected from alkyl, substituted alkyl, hydroxyl, alkoxyl, fluorine-containing thiazolinyl, cyano group and nitro;
X
1Be selected from key, O, S, SO, SO
2, CO, NR
2And R
3
X
2Be selected from O, S and NR
2,
Wherein:
R
2Be selected from hydrogen, alkyl, substituted alkyl, aryl and substituted aryl; And
R
3Be selected from alkylidene, substituted alkylene, aryl and substituted aryl;
Ar is selected from aryl and substituted aryl;
B is 1, the inferior cyclobutyl of 2-perfluor;
T is the integer of 1-3;
M is 0 to 1000 integer;
P is the integer of 1-1000; And
Q is the integer of 1-5.
9. the process of claim 1 wherein that the processing of described 100% liquid precursor material of solidifying comprises is selected from following processes:
(a) solidification process, wherein said solidification process comprises the process that is selected from thermal process, photochemistry and irradiation process, and wherein said irradiation process comprises with the described liquid precursor of radiation exposure that is selected from gamma-rays and electron beam;
(b) chemical modification process, wherein said chemical modification process comprises cross-linking process;
(c) process of formation network; And
(d) combination of said process.
10. the polymer dielectric that comprises 100% liquid precursor material of solidifying, wherein said 100% liquid precursor material of solidifying comprises the polymerizable material of about 70 weight % to about 100 weight %.
11. the polymer dielectric of claim 10, wherein said polymer dielectric has equivalent weight, and wherein said equivalent weight is selected from less than about 1500 and greater than about 1000 equivalent weight, less than about 1000 and greater than about 800 equivalent weight, less than about 800 and greater than in about 500 the equivalent weight and about equivalent weight below 500.
12. comprise the electrochemical cell of the polymer dielectric of claim 10.
13. the method for the polymer dielectric of preparation patterning, described method comprises:
(a) liquid precursor material is contacted with the ground of patterning, the ground of wherein said patterning has predetermined geometry and macro surface is long-pending; And
(b) handle described liquid precursor material, form the polymer dielectric of patterning.
14. the method for claim 13, wherein said liquid precursor material comprise the precursor that is selected from proton-conducting material, proton-conducting material and the material in their combination.
15. the method for claim 13, wherein said predetermined geometry comprises nonplanar geometry, and its size is selected from less than about 10 millimeters and greater than about 1 millimeter size, less than about 1 millimeter and greater than about 100 microns size, less than about 100 microns and greater than about 10 microns size, less than about 10 microns and greater than about 1 micron size and less than in about 1 micron size.
16. the method for claim 13, wherein said predetermined geometry are by catalyst layer and one of comprise in the electrode material of membrane electrode assembly and to limit.
17. the method for claim 13, wherein said predetermined geometry comprise the structure that is selected from pattern, peg, wall, cross one another surface and the curling cylinder.
18. the method for claim 13, wherein said predetermined geometry comprise that its surface area is greater than the long-pending structure of the macro surface of described patterning ground.
19. the method for claim 13 wherein comprises the processing of described liquid precursor material being selected from following processes:
(a) solidification process;
(b) chemical modification process;
(c) process of formation network;
(d) solvent evaporation process; And
(e) combination of said process.
20. proton exchange membrane by the patterning of the method for claim 13 preparation.
21. comprise the electrochemical cell of proton exchange membrane of the patterning of claim 20.
22. preparation has the method for the polymer dielectric of a plurality of equivalent weights, described method comprises:
(a) on ground, use first liquid precursor material with first equivalent weight;
(b) handle described first liquid precursor material, on ground, form the liquid precursor material that ground floor is handled;
(c) on the treated liquid precursor material of the ground floor on the ground, use second liquid precursor material with second equivalent weight; And
(d) handle described second liquid precursor material, form polymer dielectric with a plurality of equivalent weights.
23. the method for claim 22, wherein said first liquid precursor material, second liquid precursor material are selected from the precursor and their combination of proton-conducting material, proton-conducting material.
24. the method for claim 22, wherein said first equivalent weight is greater than described second equivalent weight.
25. the method for claim 22, wherein said ground is selected from anode and negative electrode.
26. the method for claim 22, it comprises with the predetermined multiple liquid precursor material repeating step (c) with a plurality of equivalent weights to (d), formation has the polymer dielectric of a plurality of equivalent weights, and wherein said multiple liquid precursor material is selected from the precursor and their combination of proton-conducting material, proton-conducting material.
27. polymer dielectric with a plurality of equivalent weights by the preparation of the method for claim 22.
28, the electrochemical cell that comprises the polymer dielectric of claim 27.
29. form the method for membrane electrode assembly (MEA), described method comprises:
(a) provide the proton exchange membrane of patterning;
(b) provide first catalyst material and second catalyst material;
(c) provide first electrode material and second electrode material;
(d) mode that is communicated with conduction is operationally settled described proton exchange membrane, described first and second catalyst materials and described first and second electrode materials, forms membrane electrode assembly.
30. the method for claim 29 at least aly in wherein said first catalyst material and second catalyst material comprises accessible catalyst ink water composition.
31. the method for claim 30, wherein said accessible catalyst ink water composition comprises liquid precursor material and mixture of catalysts.
32. the method for claim 31, wherein said liquid precursor material comprise the liquid PFPE material with chemically stable end group.
33. the method for claim 31, wherein said catalyst comprise the metal that is selected from platinum, ruthenium, molybdenum, chromium and their combination.
34. the method for claim 30, wherein said accessible catalyst ink water composition comprises carbon black.
35. the method for claim 30, it comprises described accessible catalyst ink water composition is administered in the proton exchange membrane and first and second electrode materials at least one.
36. the method for claim 35, it comprises described accessible catalyst ink water composition conformally is administered in the proton exchange membrane and first and second electrode materials at least one.
37. the method for claim 35, using of wherein said accessible catalyst ink water composition comprises the method that is selected from following group: CVD method, flame atomizing deposition process, ink jet printing method and pulse laser desorption method that chemical vapor deposition (CVD) method, method of electrospraying, electric field desorption method, radio frequency plasma strengthen.
38. the method for claim 29, wherein said electrode material is selected from carbon cloth, carbon paper and the carbon black.
39. the method for claim 38, it comprises the patterning of electrode material, and the patterning of wherein said electrode material comprises the following process that is selected from:
(a) photoetching process;
(b) electron-beam direct writing process;
(c) make with photoresist electron beam lithography process; And
(d) plasma etch process of use mask.
40. the membrane electrode assembly (MEA) that forms by the method for claim 29.
41. prepare the method for membrane electrode assembly, described method comprises:
(a) provide first electrode material;
(b) provide second electrode material;
(c) settle described first electrode material and second electrode material in the spatial placement mode that between described first electrode material and second electrode material, forms spacing;
(d) arrange liquid precursor material in the spacing between described first electrode material and second electrode material; And
(e) handle described liquid precursor material, form membrane electrode assembly.
42. the method for claim 41, wherein said liquid precursor material are selected from the precursor of proton-conducting material, proton-conducting material and their combination.
43. the membrane electrode assembly (MEA) that forms by the method for claim 41.
44. form the method for electrochemical cell, described method comprises:
(a) provide one deck PFPE (PFPE) material at least, it comprises at least one fluid channel;
(b) provide first electrode material and second electrode material;
(c) provide first catalyst material and second catalyst material;
(d) provide proton exchange membrane; And
(e) operationally settle the described PFPE of one deck at least material, described first electrode material, described second electrode material, described first catalyst material, described second catalyst material and described proton exchange membrane, thereby form electrochemical cell.
45. the method for claim 44, it comprises provides:
(a) PFPE of ground floor photocuring (PFPE), it comprises at least one first fluid channel that is communicated with the described first electrode fluid; And
(b) PFPE of second layer photocuring (PFPE), it comprises at least one second fluid channel that is communicated with the described second electrode fluid.
46. the method for claim 44, wherein said at least one fluid channel has inlet.
47. the method for claim 46, wherein said inlet is communicated with the fuels sources fluid.
48. the method for claim 47, wherein said fuels sources comprises methyl alcohol.
49. comprising, the method for claim 47, wherein said fuels sources contain oxygen (O
2) gas.
50. the method for claim 44, wherein said at least one fluid channel has outlet.
51. the method for claim 50, wherein said outlet and fuel recycle passage and refuse outlet one of at least fluid are communicated with.
52. the method for claim 44, wherein said at least one fluid channel comprises valve.
53. the method for claim 44, it comprises the fluid channel network.
54. the method for claim 44, being selected from carbon cloth, carbon paper and the carbon black one of at least in wherein said first electrode material and second electrode material.
55. the method for claim 44, wherein said first electrode material:
(a) with described first catalyst material coating;
(b) with described first catalyst material dipping; Perhaps
(c) above-mentioned combination.
56. the method for claim 44, wherein said second electrode material:
(a) with described second catalyst material coating;
(b) with described second catalyst material dipping; Perhaps
(c) above-mentioned combination.
57. the method for claim 44 comprises one of at least the metal that is selected from platinum, ruthenium, molybdenum, chromium and their combination in wherein said first catalyst material and second catalyst material.
58. comprising, the method for claim 44, wherein said proton exchange membrane be selected from following liquid precursor material:
(a) derivative of sulfonic acid material;
(b) PFPE (PFPE) material; And
(c) their combination.
59. the method for claim 44, it comprise make at least one electricity output connect with described first electrode material and second electrode material in be operably connected one of at least.
60. the electrochemical cell that forms by the method for claim 44.
61. the method for operation electrochemical cell, described method comprises:
(a) provide and comprise the electrochemical cell of one deck PFPE (PFPE) material at least, described PFPE material layer comprises at least one fluid channel;
(b) the first electrode reaction thing and the second electrode reaction thing are assigned in the electrochemical cell; And
(c) from described electrochemical cell, produce electricity output.
62. the method for claim 61, the wherein said first electrode reaction thing is selected from H
2, alkane, alkylol, dialkyl ether and glycol.
63. the method for claim 61, the wherein said second electrode reaction thing is selected from and contains oxygen (O
2) gas.
64. the method for claim 61, it comprises that the electricity output of guiding described electrochemical cell provides power to equipment, and wherein said equipment is selected from generator, portable instrument, electric tool, road sign, stand-by power supply, consumer electronics, Military Electronic Equipment, automobile equipment and non-automobile individual vehicle.
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| US53870604P | 2004-01-23 | 2004-01-23 | |
| US60/538,706 | 2004-01-23 | ||
| US60/538,878 | 2004-01-23 |
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| CN (1) | CN101390244A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102484260A (en) * | 2010-02-04 | 2012-05-30 | 松下电器产业株式会社 | A method for fabricating a polymer electrolyte membrane for a fuel cell |
| CN102598389A (en) * | 2009-06-24 | 2012-07-18 | 丰田自动车工程及制造北美公司 | High voltage electrolyte |
| CN103774263A (en) * | 2012-10-24 | 2014-05-07 | 通用汽车环球科技运作有限责任公司 | PFCB nanometer scale fibers |
| CN106953112A (en) * | 2017-05-09 | 2017-07-14 | 广东工业大学 | A kind of three-diemsnional electrode material preparation method and application |
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2005
- 2005-01-21 CN CNA2005800092318A patent/CN101390244A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102598389A (en) * | 2009-06-24 | 2012-07-18 | 丰田自动车工程及制造北美公司 | High voltage electrolyte |
| CN102598389B (en) * | 2009-06-24 | 2015-04-01 | 丰田自动车工程及制造北美公司 | High voltage electrolyte |
| CN102484260A (en) * | 2010-02-04 | 2012-05-30 | 松下电器产业株式会社 | A method for fabricating a polymer electrolyte membrane for a fuel cell |
| CN102484260B (en) * | 2010-02-04 | 2015-11-25 | 松下知识产权经营株式会社 | For the manufacture of the method for polymer electrolyte membrane for fuel cell |
| CN103774263A (en) * | 2012-10-24 | 2014-05-07 | 通用汽车环球科技运作有限责任公司 | PFCB nanometer scale fibers |
| CN106953112A (en) * | 2017-05-09 | 2017-07-14 | 广东工业大学 | A kind of three-diemsnional electrode material preparation method and application |
| CN106953112B (en) * | 2017-05-09 | 2019-10-29 | 广东工业大学 | A kind of three-diemsnional electrode material preparation method and application |
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