CN1848504A - Composite proton exchange membrane for high-temperature fuel battery and producing method thereof - Google Patents
Composite proton exchange membrane for high-temperature fuel battery and producing method thereof Download PDFInfo
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- CN1848504A CN1848504A CNA2005100461776A CN200510046177A CN1848504A CN 1848504 A CN1848504 A CN 1848504A CN A2005100461776 A CNA2005100461776 A CN A2005100461776A CN 200510046177 A CN200510046177 A CN 200510046177A CN 1848504 A CN1848504 A CN 1848504A
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- proton exchange
- exchange membrane
- membrane
- compound
- phosphoric acid
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- 239000012528 membrane Substances 0.000 title claims abstract description 58
- 239000000446 fuel Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 4
- 239000002131 composite material Substances 0.000 title claims description 7
- 229920002480 polybenzimidazole Polymers 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 23
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 19
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 18
- 125000004104 aryloxy group Chemical group 0.000 claims description 18
- 238000006277 sulfonation reaction Methods 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052726 zirconium Inorganic materials 0.000 claims description 16
- 238000010345 tape casting Methods 0.000 claims description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012965 benzophenone Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000001235 sensitizing effect Effects 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000166 zirconium phosphate Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000004693 Polybenzimidazole Substances 0.000 abstract 2
- 238000005266 casting Methods 0.000 abstract 1
- QOKYJGZIKILTCY-UHFFFAOYSA-J hydrogen phosphate;zirconium(4+) Chemical compound [Zr+4].OP([O-])([O-])=O.OP([O-])([O-])=O QOKYJGZIKILTCY-UHFFFAOYSA-J 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 11
- 239000007789 gas Substances 0.000 description 8
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 4
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a high-temperature proton exchange membrane fuel cell compound membrane. In the concrete, it is a compound proton exchange membrane for high-temperature proton exchange membrane fuel cell using hydrogen and methyl alcohol as fuel and its preparation method. Said preparation method includes the following steps: making the mixture of heteropolyacid and zirconium hydrogen phosphate and polybenzimidazole (PBI) or sulfonated polyacryloxyphosphonitrile undergo the process of adulteration, preparing compound proton exchange membrane material, and utilizing doctor-blade casting process to form membrane.
Description
Technical field
The present invention relates to the high temperature proton exchange film fuel cell composite membrane, specifically a kind of high temperature proton exchange film fuel cell polymer-inorganic composite proton exchange membrane and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of Blast Furnace Top Gas Recovery Turbine Unit (TRT) that the chemical energy in fuel and the oxidant is directly changed into electric energy by electrochemical reaction.It is to be electrolyte with the solid polymer membrane with good proton-conducting, the anode that one side of film is made up of Catalytic Layer and gas diffusion layers, the negative electrode that opposite side is made up of Catalytic Layer and gas diffusion layers, be Catalytic Layer between gas diffusion layers and proton exchange membrane, pole catalyze layer provides electrochemical reaction.Anode, solid polymer electrolytic film and negative electrode three press together and constitute Proton Exchange Membrane Fuel Cells (PEMFC) core component---membrane electrode three-in-one (MEA), the three-in-one both sides of membrane electrode are provided with the graphite cake of gas flow channel or surface modification of metals plate (bipolar plates) back constitutes the Proton Exchange Membrane Fuel Cells monocell, and several are superimposed and constitute pile in the filter press mode to hundreds of monocells.During oxidants such as fuel such as antianode hydrogen supply or reformation gas, target supply oxygen or air, go up the generation electrochemical reaction, the chemical energy in fuel and the oxidant is converted into electric energy at membrane electrode three-in-one (MEA).
The proton exchange membrane of proton exchange membrane is the PEMFC critical component, and it directly influences battery performance and life-span.The proton exchange membrane that is used for PEMFC must satisfy following condition:
(1) has high H
+Conducting power, generally speaking conductivity will reach the order of magnitude of 0.01S/cm;
(2) under the condition of PEMFC operation promptly in battery operated temperature, under the operating potential of oxidation and reducing atmosphere and electrode, membrane structure and resin composition remain unchanged, and promptly have good chemistry and electrochemical stability;
(3) no matter film all should have the infiltration coefficient of low reacting gas such as hydrogen, oxygen at dry state or hygrometric state (full suction), guarantee that battery has high faraday (enclosed pasture) efficient; Generally speaking, the gas permeability coefficient of film＜10
-8Cm
3Cmcm
-2Sec
-1CmHg
-1
(4) a certain temperature before the film resin decomposition temperature such as vitrifying or near vitrification point, the film surface has certain viscoplasticity combine the minimizing contact resistance in order to electrocatalyst layers when the preparation membrane electrode is three-in-one and film;
(5) no matter at dry state or hygrometric state, film all should have certain mechanical strength, is suitable for the assembling of three-in-one preparation of membrane electrode and battery pack.
At present, people just are being devoted to develop high temperature proton exchange film, because along with the raising in proton exchange membrane work allowable temperature interval, bring a series of benefit to PEMFC, aspect electrochemistry, show as: help CO and pay with taking off, improve anti-CO ability in the oxidation of anode; Reduce the redox overpotential of negative electrode; Improve activity of such catalysts; Improve the proton conductive ability of film.Show as in system and utilization side heat: simplified cooling system; Can effectively utilize used heat; Reduce reforming system steam use amount.Along with the intensification of people to high temperature proton exchange film fuel cell understanding, the heat-resisting proton exchange membrane of development of new is paid attention to by increasing research worker.
Summary of the invention
In order to develop high temperature proton exchange film fuel cell, the invention provides a kind of high temperature proton exchange film fuel cell with widely-used temperature (room temperature-200 ℃) with composite membrane and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is:
A kind of used for high-temperature fuel cell polymer-inorganic composite proton exchange membrane and preparation method thereof can prepare according to the following procedure,
A) the poly-aryloxy group phosphonitrile of polybenzimidazoles (PBI) or sulfonation is dissolved in polar solvent (for example: N-methyl pyrrolidone, N, N-dimethylacetylamide, dimethyl sulfoxide (DMSO))) in, it is standby to be mixed with volumetric concentration 5～80% Polymer Solutions;
B) at the heteropoly acid and/or the phosphoric acid hydrogen zirconium of above-mentioned Polymer Solution adding polybenzimidazoles (PBI) or the poly-aryloxy group phosphonitrile weight 20～80% of sulfonation, stir, make the proton exchange coating solution;
C) for containing polybenzimidazoles (PBI) proton exchange coating solution, use The tape casting, coating method or cement-dipping method obtain required proton exchange membrane;
For the proton exchange coating solution that contains the poly-aryloxy group phosphonitrile of sulfonation, add benzophenone and make sensitising agent, use The tape casting, make it crosslinked with UV-irradiation after coating method or the cement-dipping method film forming, obtain required proton exchange membrane.
Described heteropoly acid is meant the Cs with proton exchange function
xH
3-xBM
12Compound, wherein, X=0-3, B=P, Si or As, M=Mo, W or V; Phosphoric acid hydrogen zirconium is meant Zr
xH
3-2xPO
4Compounds, wherein, X=0-1.5,10nm≤particle size≤200nm; Described when above-mentioned Polymer Solution adds heteropoly acid and/or phosphoric acid hydrogen zirconium, (for example: N-methyl pyrrolidone, N, N-dimethylacetylamide, dimethyl sulfoxide (DMSO)) wiring solution-forming or suspension in polar solvent with heteropoly acid and/or phosphoric acid hydrogen zirconium earlier; The UV-irradiation time is preferably more than 30 minutes or 30 minutes.
The present invention has compared following advantage with existing material with technology:
1. the proton exchange ability of film is strong.The purpose of doping phosphoric acid hydrogen zirconium of the present invention and heteropoly acid is to improve the proton conductivity of film, in the hope of reaching the requirement of PEMFC battery to film; The compound proton exchange membrane that utilizes preparation method proposed by the invention to make all has excellent proton exchange ability at low temperature and high temperature.
2. the good stability of film.The poly-aryloxy group phosphonitrile of polybenzimidazoles (PBI) or sulfonation is a kind of polymer that can catch proton fast, has good chemical stability and thermal stability; The compound proton exchange membrane that utilizes preparation method proposed by the invention to make has good chemical stability (heat decomposition temperature＞350 ℃) and good alcohol-rejecting ability.The prepared proton exchange membrane of the present invention all can be used in room temperature-200 ℃ scope, has serviceability temperature widely.
3. preparation technology is simple, and cost is low.The present invention mixes up heteropoly acid and phosphoric acid hydrogen zirconium mixture and polybenzimidazoles (PBI) or the poly-aryloxy group phosphonitrile of sulfonation, preparation compoiste proton exchange film material, by the The tape casting film forming, compound proton exchange membrane preparation technology is simple then, and the cost of material is low is easy to industrialization; Compound proton exchange membrane of the present invention can be used in the high temperature proton exchange film fuel cell (as: be with hydrogen fuel and be the high temperature proton exchange film fuel cell of raw material with methyl alcohol), and it will promote the development of high temperature proton exchange film fuel cell.
Embodiment
Embodiment 1
Add the phosphoric acid hydrogen zirconium powder end (particle diameter 30nm) that is equivalent to phosphotungstic acid weight 50% in the N-of phosphotungstic acid methyl pyrrolidone in the solution, ultrasonic (frequency: 4000 hertz) mixed in 24 hours.A certain amount of polybenzimidazoles (PBI) is dissolved in to be mixed with volumetric concentration in the N-methyl pyrrolidone in the solution be that 70% Polymer Solution is standby.The suspension that the Polymer Solution and the weight of polybenzimidazoles (PBI) is equivalent to its 50% phosphotungstic acid and phosphoric acid hydrogen zirconium mixes.Be heated to 150 ℃ and stirred (200 revolutions per seconds of clocks) 1 hour down.Make the proton exchange coating solution.Obtain required proton exchange membrane with the The tape casting film forming; The thickness of film is 0.050mm.
Embodiment 2
At the N of phosphomolybdic acid, add the phosphoric acid hydrogen zirconium powder end (particle diameter 200nm) that is equivalent to phosphomolybdic acid weight 100% in the N-dimethylacetylamide in the solution, ultrasonic (frequency: 4000 hertz) mixed in 24 hours.The poly-aryloxy group phosphonitrile of a certain amount of sulfonation is dissolved in to be mixed with volumetric concentration in the N-methyl pyrrolidone in the solution be that 40% Polymer Solution is standby.The Polymer Solution of the poly-aryloxy group phosphonitrile of sulfonation and the suspension that weight is equivalent to its 50% phosphomolybdic acid and phosphoric acid hydrogen zirconium are mixed.Be heated to 150 ℃ and stirred (200 revolutions per seconds of clocks) 2 hours, ultrasonic then (frequency: 4000 hertz) 12 hours down.Make the proton exchange coating solution.Add benzophenone and make sensitising agent,, obtain required proton exchange membrane with making it crosslinked with UV-irradiation after the The tape casting film forming.The thickness of film is 0.10mm.
Embodiment 3
Add the γ-basic zirconium phosphate powder (particle diameter 100nm) that is equivalent to phosphomolybdic acid weight 50% in the dimethyl sulfoxide (DMSO) of phosphomolybdic acid in the solution, ultrasonic (frequency: 4000 hertz) mixed in 24 hours.A certain amount of polyphenylene oxides phosphonitrile is dissolved in to be mixed with volumetric concentration in the N-methyl pyrrolidone in the solution be that 30% Polymer Solution is standby.The Polymer Solution of the poly-aryloxy group phosphonitrile of sulfonation and the suspension that weight is equivalent to its phosphomolybdic acid of 50% and γ-basic zirconium phosphate are mixed.Be heated to 120 ℃ and stir (200 revolutions per seconds of clocks), ultrasonic then (frequency: 4000 hertz) 12 hours down., make the proton exchange coating solution.Add sensitising agent (as benzophenone etc.),, obtain required proton exchange membrane with making it crosslinked with UV-irradiation after the The tape casting film forming.The thickness of film is 0.075mm.
Embodiment 4
Add the γ-basic zirconium phosphate powder (particle diameter 50nm) that is equivalent to silico-tungstic acid weight 50% in the N-of silico-tungstic acid methyl pyrrolidone in the solution, ultrasonic (frequency: 4000 hertz) mixed in 24 hours.A certain amount of polybenzimidazoles (PBI) is dissolved in to be mixed with volumetric concentration in the N-methyl pyrrolidone in the solution be that 20% Polymer Solution is standby.The suspension that the Polymer Solution and the weight of polybenzimidazoles (PBI) is equivalent to its silico-tungstic acid of 50% and γ-basic zirconium phosphate mixes.Be heated to 150 ℃ and stirred (200 revolutions per seconds of clocks) 1 hour down., make the proton exchange coating solution.After the The tape casting film forming, obtain required proton exchange membrane.The thickness of film is 0.065mm
Embodiment 5
The poly-aryloxy group phosphonitrile of a certain amount of sulfonation is dissolved in N, and it is standby to be mixed with volumetric concentration in the N-dimethylacetamide solution and to be 20% Polymer Solution.The phosphotungstic acid that then weight is equivalent to the poly-aryloxy group phosphonitrile 80% of its sulfonation adds in this Polymer Solution.Be heated to 150 ℃ and stir (200 revolutions per seconds of clocks) down, make the proton exchange coating solution.Add benzophenone and make sensitising agent,, obtain required proton exchange membrane with making it crosslinked with UV-irradiation 40min after the The tape casting film forming.The thickness of film is 0.035mm
Embodiment 6
The poly-aryloxy group phosphonitrile of a certain amount of sulfonation is dissolved in N, and it is standby to be mixed with volumetric concentration in the N-dimethylacetamide solution and to be 50% Polymer Solution.The Cs that then weight is equivalent to the poly-aryloxy group phosphonitrile 80% of its sulfonation
2.5H
0.5PW
12Add in this Polymer Solution.Be heated to 150 ℃ and stir (200 revolutions per seconds of clocks) down, make the proton exchange coating solution.Add benzophenone and make sensitising agent,, obtain required proton exchange membrane with making it crosslinked with UV-irradiation 80min after the The tape casting film forming.The thickness of film is 0.025mm
Embodiment 7
With a certain amount of polybenzimidazoles (PBI)) be dissolved in that to be mixed with volumetric concentration in the N-methyl pyrrolidone in the solution be that 70% Polymer Solution is standby.The Polymer Solution and the weight of polybenzimidazoles (PBI) are equivalent to its Cs of 30%
2.5H
0.5PW
12, be heated to 120 ℃ and stirred (200 revolutions per seconds of clocks) 2 hours down., make the proton exchange coating solution.Add sensitising agent (as benzophenone etc.), with obtaining required proton exchange membrane after the The tape casting film forming.The thickness of film is 0.095mm.
Embodiment 8
With a certain amount of polybenzimidazoles (PBI)) be dissolved in that to be mixed with volumetric concentration in the N-methyl pyrrolidone in the solution be that 70% Polymer Solution is standby.The Polymer Solution and the weight of polybenzimidazoles (PBI) are equivalent to its silico-tungstic acid of 80%, are heated to 120 ℃ and stirred (200 revolutions per seconds of clocks) 2 hours down, make the proton exchange coating solution.With obtaining required proton exchange membrane after the The tape casting film forming.The thickness of film is 0.050mm.
Claims (8)
1. composite proton exchange membrane for high-temperature fuel battery is characterized in that: can prepare according to the following procedure,
A) the poly-aryloxy group phosphonitrile of polybenzimidazoles or sulfonation is dissolved in the polar solvent, it is standby to be mixed with volumetric concentration 5～80% Polymer Solutions;
B) at the heteropoly acid and/or the phosphoric acid hydrogen zirconium of above-mentioned Polymer Solution adding polybenzimidazoles or the poly-aryloxy group phosphonitrile weight 20～80% of sulfonation, stir, make the proton exchange coating solution;
C) for containing polybenzimidazoles proton exchange coating solution, use The tape casting, coating method or cement-dipping method obtain required proton exchange membrane;
For the proton exchange coating solution that contains the poly-aryloxy group phosphonitrile of sulfonation, add benzophenone and make sensitising agent, use The tape casting, make it crosslinked with UV-irradiation after coating method or the cement-dipping method film forming, obtain required proton exchange membrane.
2. compound proton exchange membrane according to claim 1 is characterized in that: described heteropoly acid is meant the Cs with proton exchange function
xH
3-xBM
12Compound, wherein, X=0-3, B=P, Si or As, M=Mo, W or V;
Described phosphoric acid hydrogen zirconium is meant Zr
XH
3-2XPO
4Compounds, wherein, X=0-1.5,10nm≤particle size≤200nm.
3. compound proton exchange membrane according to claim 1 is characterized in that: described when above-mentioned Polymer Solution adds heteropoly acid and/or phosphoric acid hydrogen zirconium, and wiring solution-forming or suspension in polar solvent with heteropoly acid and/or phosphoric acid hydrogen zirconium earlier.
4. compound proton exchange membrane according to claim 1 is characterized in that: the described UV-irradiation time is more than 30 minutes or 30 minutes.
5 one kinds of described membrane cells of claim 1 preparation method of compound proton exchange membrane is characterized in that: can operate as follows,
A) the poly-aryloxy group phosphonitrile of polybenzimidazoles (PBI) or sulfonation being dissolved in the polar solvent (for example: N-methyl pyrrolidone, N, N-dimethylacetylamide, dimethyl sulfoxide (DMSO)), to be mixed with volumetric concentration 5～80% Polymer Solutions standby;
B) at the heteropoly acid and/or the phosphoric acid hydrogen zirconium of above-mentioned Polymer Solution adding polybenzimidazoles (PBI) or the poly-aryloxy group phosphonitrile weight 20～100% of sulfonation, stir, make the proton exchange coating solution;
C) for containing polybenzimidazoles (PBI) proton exchange coating solution, use The tape casting, coating method or cement-dipping method obtain required proton exchange membrane;
For the proton exchange coating solution that contains the poly-aryloxy group phosphonitrile of sulfonation, add benzophenone and make sensitising agent, use The tape casting, make it crosslinked with UV-irradiation after coating method or the cement-dipping method film forming, obtain required proton exchange membrane.
6. according to the preparation method of the described membrane cell of claim 5 with compound proton exchange membrane, it is characterized in that: described heteropoly acid is meant the Cs with proton exchange function
xH
3-xBM
12Compound, wherein, X=0-3, B=P, Si or As, M=Mo, W or V;
Described phosphoric acid hydrogen zirconium is meant Zr
XH
3-2XPO
4Compounds, wherein, X=0-1.5,10nm≤particle size≤200nm.
7. according to the preparation method of the described membrane cell of claim 5 with compound proton exchange membrane, it is characterized in that: described when above-mentioned Polymer Solution adds heteropoly acid and/or phosphoric acid hydrogen zirconium, wiring solution-forming or suspension in polar solvent with heteropoly acid and/or phosphoric acid hydrogen zirconium earlier.
8. according to the preparation method of the described membrane cell of claim 5 with compound proton exchange membrane, it is characterized in that: the described UV-irradiation time is more than 30 minutes or 30 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100461776A CN100365858C (en) | 2005-04-05 | 2005-04-05 | Composite proton exchange membrane for high-temperature fuel battery and producing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100461776A CN100365858C (en) | 2005-04-05 | 2005-04-05 | Composite proton exchange membrane for high-temperature fuel battery and producing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1848504A true CN1848504A (en) | 2006-10-18 |
| CN100365858C CN100365858C (en) | 2008-01-30 |
Family
ID=37077965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| CNB2005100461776A Expired - Fee Related CN100365858C (en) | 2005-04-05 | 2005-04-05 | Composite proton exchange membrane for high-temperature fuel battery and producing method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101170181B (en) * | 2006-10-25 | 2010-08-11 | 新源动力股份有限公司 | A compound proton exchange film for self-humidity increase fuel battery and its making method |
| CN102044648A (en) * | 2009-10-16 | 2011-05-04 | 中国科学院大连化学物理研究所 | Poly(arylene ether benzimidazole) ion exchange membrane and preparation method thereof and all-vanadium redox flow battery |
| CN103846021A (en) * | 2012-12-05 | 2014-06-11 | 中国科学院大连化学物理研究所 | Separation membrane material as well as synthesis and application thereof |
| CN103887536A (en) * | 2014-03-13 | 2014-06-25 | 清华大学 | Method for preparing polybenzimidazole proton exchange membrane subjected to inorganic material hybridization |
| CN104475155A (en) * | 2014-12-03 | 2015-04-01 | 中国石油天然气股份有限公司 | Catalyst for selective oxidation desulfurization of fuel oil as well as preparation method and application of catalyst |
| CN107221692A (en) * | 2016-09-27 | 2017-09-29 | 黄河科技学院 | A kind of polybenzimidazoles with high anti-oxidation ability/phosphoric acid MULTILAYER COMPOSITE high temperature proton exchange film and preparation method thereof |
| CN108666602A (en) * | 2018-05-17 | 2018-10-16 | 北京化工大学 | A kind of alkali resistance anion-exchange membrane and preparation method thereof of load substituted imidazole unit |
| CN109888348A (en) * | 2019-04-10 | 2019-06-14 | 黑龙江大学 | Fuel cell proton membrane material solid super acids/azacyclo- graphene oxide/2,5- polybenzimidazoles preparation method |
| CN111205640A (en) * | 2020-01-11 | 2020-05-29 | 山东理工大学 | Preparation of cyclotriphosphazene hexaphosphate doped polybenzimidazole proton exchange membrane |
| CN111205495A (en) * | 2020-01-11 | 2020-05-29 | 山东理工大学 | Preparation of novel polybenzimidazole high-temperature low-humidity proton exchange membrane doped with poly (diphosphophosphazene) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6365294B1 (en) * | 1999-04-30 | 2002-04-02 | The Administrators Of The Tulane Educational Fund | Sulfonated polyphosphazenes for proton-exchange membrane fuel cells |
| US6987163B2 (en) * | 2002-08-07 | 2006-01-17 | Research Foundation Of The State University Of New York | Modified polybenzimidazole (PBI) membranes for enhanced polymer electrochemical cells |
| CN1252842C (en) * | 2004-02-06 | 2006-04-19 | 清华大学 | Process for preparing odified sulfonic acid lateral group polybenzimidazoles proton interchange films |
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- 2005-04-05 CN CNB2005100461776A patent/CN100365858C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101170181B (en) * | 2006-10-25 | 2010-08-11 | 新源动力股份有限公司 | A compound proton exchange film for self-humidity increase fuel battery and its making method |
| CN102044648A (en) * | 2009-10-16 | 2011-05-04 | 中国科学院大连化学物理研究所 | Poly(arylene ether benzimidazole) ion exchange membrane and preparation method thereof and all-vanadium redox flow battery |
| CN102044648B (en) * | 2009-10-16 | 2013-04-10 | 大连融科储能技术发展有限公司 | Poly(arylene ether benzimidazole) ion exchange membrane and preparation thereof and all-vanadium redox flow battery |
| CN103846021B (en) * | 2012-12-05 | 2016-12-21 | 中国科学院大连化学物理研究所 | A kind of separation membrane material its synthesis and application |
| CN103846021A (en) * | 2012-12-05 | 2014-06-11 | 中国科学院大连化学物理研究所 | Separation membrane material as well as synthesis and application thereof |
| CN103887536A (en) * | 2014-03-13 | 2014-06-25 | 清华大学 | Method for preparing polybenzimidazole proton exchange membrane subjected to inorganic material hybridization |
| CN104475155A (en) * | 2014-12-03 | 2015-04-01 | 中国石油天然气股份有限公司 | Catalyst for selective oxidation desulfurization of fuel oil as well as preparation method and application of catalyst |
| CN107221692A (en) * | 2016-09-27 | 2017-09-29 | 黄河科技学院 | A kind of polybenzimidazoles with high anti-oxidation ability/phosphoric acid MULTILAYER COMPOSITE high temperature proton exchange film and preparation method thereof |
| CN107221692B (en) * | 2016-09-27 | 2019-10-22 | 中科院大连化学物理研究所张家港产业技术研究院有限公司 | A kind of polybenzimidazoles with high anti-oxidation ability/phosphoric acid MULTILAYER COMPOSITE high temperature proton exchange film and preparation method thereof |
| CN108666602A (en) * | 2018-05-17 | 2018-10-16 | 北京化工大学 | A kind of alkali resistance anion-exchange membrane and preparation method thereof of load substituted imidazole unit |
| CN109888348A (en) * | 2019-04-10 | 2019-06-14 | 黑龙江大学 | Fuel cell proton membrane material solid super acids/azacyclo- graphene oxide/2,5- polybenzimidazoles preparation method |
| CN109888348B (en) * | 2019-04-10 | 2021-10-08 | 黑龙江大学 | Preparation method of fuel cell proton membrane material solid super acid/aza-epoxidized graphene/2, 5-polybenzimidazole |
| CN111205640A (en) * | 2020-01-11 | 2020-05-29 | 山东理工大学 | Preparation of cyclotriphosphazene hexaphosphate doped polybenzimidazole proton exchange membrane |
| CN111205495A (en) * | 2020-01-11 | 2020-05-29 | 山东理工大学 | Preparation of novel polybenzimidazole high-temperature low-humidity proton exchange membrane doped with poly (diphosphophosphazene) |
| CN111205495B (en) * | 2020-01-11 | 2022-07-26 | 山东理工大学 | Preparation method of poly (diphosphophosphazene) doped polybenzimidazole proton exchange membrane with high temperature and low humidity |
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