CN112086672B - 一种燃料电池用复合型高温质子交换膜及其制备方法和应用 - Google Patents
一种燃料电池用复合型高温质子交换膜及其制备方法和应用 Download PDFInfo
- Publication number
- CN112086672B CN112086672B CN202010969077.5A CN202010969077A CN112086672B CN 112086672 B CN112086672 B CN 112086672B CN 202010969077 A CN202010969077 A CN 202010969077A CN 112086672 B CN112086672 B CN 112086672B
- Authority
- CN
- China
- Prior art keywords
- temperature
- proton exchange
- exchange membrane
- compound
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 239000000446 fuel Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 238000002791 soaking Methods 0.000 claims abstract description 24
- 238000005266 casting Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 239000002135 nanosheet Substances 0.000 claims abstract description 14
- 229940126062 Compound A Drugs 0.000 claims abstract description 13
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 150000003254 radicals Chemical class 0.000 claims abstract description 11
- 238000010791 quenching Methods 0.000 claims abstract description 8
- 230000000171 quenching effect Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 4
- 239000005357 flat glass Substances 0.000 claims abstract description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 38
- 239000004693 Polybenzimidazole Substances 0.000 claims description 36
- 229920002480 polybenzimidazole Polymers 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 29
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003880 polar aprotic solvent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- DPZVOQSREQBFML-UHFFFAOYSA-N 3h-pyrrolo[3,4-c]pyridine Chemical compound C1=NC=C2CN=CC2=C1 DPZVOQSREQBFML-UHFFFAOYSA-N 0.000 claims description 2
- 239000002241 glass-ceramic Substances 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 19
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 16
- 239000002585 base Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 14
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000013183 functionalized metal-organic framework Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2287—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1097—Fuel cells applied on a support, e.g. miniature fuel cells deposited on silica supports
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Fuel Cell (AREA)
- Conductive Materials (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
本发明属于质子交换膜燃料电池技术领域,具体涉及一种燃料电池用复合型高温质子交换膜及其制备方法。其原料包括PBI、复合物A@B和磷酸,A为有自由基淬灭功能的纳米颗粒;B为纳米片状结构C3N4;复合物A@B的质量分数为0.05‑2wt.%,A@B中A与B的质量比为1:1~1:20。先制备复合物A@B,再以强极性非质子溶剂超声分散A@B,得分散液S1,再将PBI强极性非质子溶剂得到PBI溶液S2,将S1、S2均匀混合、搅拌后得到铸膜液S3,浇铸在带凹槽的平板玻璃上,干燥后将膜浸泡磷酸中,得到高温质子燃料电池用复合膜。该复合膜具有良好的机械性能、优异的电导率,并且应用于燃料电池展示出良好的性能。
Description
技术领域
本发明属于质子交换膜燃料电池技术领域,具体涉及一种燃料电池用复合型高温质子交换膜及其制备方法。
背景技术
质子交换膜燃料电池(PEMFC)是一种能够将化学能直接转化为电能的能量转换装置,只要不断地给其供给氧化剂、还原剂,就能持续的输出电能。高温质子交换膜燃料电池具有电池能量效率高、对CO的耐受能力好、水热管理系统较简单等优点,已经成为当前研究的热点问题之一。聚苯并咪唑应用于高温质子交换膜燃料电池时,必须掺杂尽可能多的磷酸,保证高的质子电导率,然而高的磷酸掺杂量又会造成力学强度的迅速下降,增加磷酸在电池运行时的流失率,影响电池的整体性能。此外掺杂的磷酸易流失,影响工作寿命,掺杂磷酸后机械强度下降,膜的尺寸稳定性降低。
为解决上述问题,专利CN106543460A公开了一种在膜内掺杂CNT@Fe3O4@C的方法,提高了质子电导率和阻隔燃料的能力,但是膜电导率的提高必须借助气体增湿。在低增湿或不增湿的条件下,难以实现复合膜性能的提升。专利CN 106188590 A公开了一种制备氨基功能化的金属有机骨架结构(I-MOFNH2),再将其掺杂到聚合物的方法,该质子交换膜在高、低湿条件下均具有优异的质子传导率,燃料渗透率低。但是MOF基材料在高温工况、浓磷酸存在的条件下易分解、稳定性差。专利CN108183250A公开了一种在膜内掺杂介孔SiO2的方法,可以提高低增湿条件下的质子传导率。但是由于SiO2本身不导质子,也无法锚固质子酸,更无法提高膜的机械强度,因此这种方法无法实现高温质子复合膜在不增湿条件下的性能。综上所述,本领域尚缺乏一种兼具高质子电导率、高机械强度、高热稳定性、高尺寸稳定性、耐氧化的高温质子交换膜。
发明内容
为解决现有技术存在的缺陷,本发明提供一种兼具良好质子电导率和力学强度的高温质子交换膜燃料电池用复合膜,并提供了其制备方法,该复合膜具有良好的机械性能、优异的电导率,并且应用于燃料电池展示出良好的性能。
为实现上述发明目的,本发明采用以下技术方案:
本发明提供一种复合型高温质子交换膜,其原料包括聚苯并咪唑、复合物A@B和磷酸,其中A为具有自由基淬灭功能的纳米颗粒;B为具有纳米片状结构的二维材料;所述复合物A@B的质量分数为0.05-2wt.%,复合物A@B中A与B的质量比为1:1~1:20。
基于以上技术方案,优选的,所述复合物A@B为A负载在B上,纳米颗粒A的直径为2-10nm;纳米片B的厚度为4-10nm。
基于以上技术方案,优选的,所述聚苯并咪唑的种类为:mPBI(聚2,2'-(间苯基)-5,5'-联苯并咪唑)、ABPBI(聚(2,5苯并咪唑))、OPBI(聚2,2'-(对二苯醚基)-5,5'-联苯并咪唑)、带磺酸基侧链的PBI、带膦酸基侧链的PBI、超支化PBI的一种或多种组合;
所述A为MnO2、Mn2O3、Fe3O4、TiO2、CeO2复合中的一种或多种;
所述B为石墨烯纳米片、BN纳米片、C3N4纳米片的一种或多种。
基于以上技术方案,优选的,所述复合物A@B为纳米颗粒的CeO2负载在纳米片状的C3N4上。
基于以上技术方案,优选的,所述复合物CeO2@C3N4的制备方法为:将二维纳米片状材料与具有自由基淬灭功能的纳米颗粒的前驱体混合,制得悬浊液;向悬浊液中加入0.5-2.5M KOH溶液,使溶液PH值为12-14,搅拌离心得到固体沉淀,用水清洗至中性,烘干后煅烧得到A@B复合物;
例如:当A为CeO2,B为片状C3N4;制备方法为:
(1)双氰胺研磨后煅烧,煅烧后研磨成粉末,分别用0.25-1.5M盐酸溶液清洗0.5-3h、去离子水清洗清洗0.5-2h,所得固体干燥备用;
(2)步骤(1)制得的固体与硝酸铈混合,制得悬浊液;向悬浊液中加入0.5-2.5MKOH溶液,使溶液PH值为12-14,搅拌离心得到固体沉淀,用水清洗至中性,烘干后煅烧得到CeO2@C3N4复合物;双氰胺与硝酸铈的质量比为15:1-5:1。
基于以上技术方案,优选的,所述煅烧条件为:从室温加热到500-600℃,升温速率为3-8℃min-1,空气气氛,升温达到设定温度后,保持3-6h;所述干燥的温度为60℃;所述步骤(2)中煅烧条件为:250℃空气氛围下煅烧2h。
本发明还提供一种上述复合型高温质子交换膜的制备方法,所述方法包括以下步骤:
(1)以强极性非质子溶剂超声分散CeO2@C3N4复合物,超声一段时间后制得分散液S1;
(2)将聚苯并咪唑(PBI)溶于强极性非质子溶剂,搅拌加热后得到PBI溶液S2;
(3)将S1、S2混合后得到铸膜液S3,S3浇铸在带凹槽的平板玻璃上,干燥后将膜浸泡磷酸中即得。
基于以上技术方案,优选的,所述步骤(1)中CeO2@C3N4复合物在分散液S1中的质量浓度为0.05-2mg/10ml;所述步骤(2)中聚苯并咪唑在溶液S2中的质量分数为0.8-5wt.%
所述步骤(1)和(2)中的非质子溶剂独立的为N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)、N-甲基-2吡咯烷酮(NMP)之中的一种或二种以上。
所述步骤(1)中超声功率为50-300W,超声时间为0.5-6h;所述步骤(3)中混合方式为磁力搅拌,搅拌功率为50-100W,搅拌时间为1-12h。
所述聚苯并咪唑膜浸渍磷酸浓度为50-85%,浸渍温度为50-150℃,浸渍时间为6-24h。
本发明还提供一种上述复合型高温质子交换膜在燃料电池中的应用。
有益效果:
(1)本发明的复合膜中,复合物表面上均匀分布的纳米颗粒可以原位淬灭生成的自由基,显著降低了对PBI主链的氧化;延长膜寿命,减缓膜的降解速度复合物主体结构中的纳米片可以充分通过酸碱锚固和物理吸附,增加磷酸吸附量,降低磷酸流失率,在膜内构筑质子传导的辅助网络可以提高质子电导率;纳米片结构可以使复合膜在质子电导率和力学强度均有较大幅度的提升,此外还起到了增强力学强度的效果;提高膜的质子传导率。
(2)本发明进一步优选为复合物为CeO2@C3N4,CeO2@C3N4复合物中的两种处于负载形式的纳米材料,可以协同作用,达到质子电导率、力学强度、耐氧化性三者的同时提高。通过调控复合物中二者的比例关系,CeO2含量适中,在C3N4表面分布较均匀,可以在不降低电导率和拉伸强度的前提下,提高对自由基的耐受性。
附图说明
图1为本发明实施例1与对比例1-2和对比例4所涉及的CeO2@C3N4纳米复合物的扫描电镜图;a.实施例1,b.对比例1,c.对比例2,d.对比例4。
图2对比例3的CeO2扫描电镜图。
具体实施方式
以下结合具体实施例对本发明作进一步说明,但不以任何方式限制本发明。专利要求书3中超支化PBI的合成方法可参考文献Journal of Membrane Science 593(2020)117435。
实施例1
以聚苯并咪唑和CeO2@C3N4为原料制备复合型高温质子交换膜,按以下步骤制备:
Step 1:称取15g双氰胺,充分研磨后置于坩埚中,随后放在管式炉中煅烧,从室温加热到550℃,升温速率为5℃min-1,空气气氛,升温达到设定温度后,保持4h,随炉降温,将其转移到研钵中仔细研磨成粉末,再分别用1M盐酸溶液清洗1.5h、去离子水清洗清洗2h,所得固体于60℃烘箱中干燥。再将所得固体与0.2g硝酸铈混合,加入50g去离子水,磁力搅拌1h,得到悬浊液。随后向悬浊液中加入1M KOH溶液,调节溶液PH值为13,磁力搅拌2h,离心得到固体沉淀。用大量去离子水清洗,直至溶液PH为中性。最后在烘箱中将物料完全干燥,250℃空气氛围下煅烧2h,得到CeO2@C3N4复合物。
Step 2:称取0.12mgCeO2@C3N4复合物,量取10ml NMP,超声功率为100W,超声4h,得到分散液S1。称取0.27gmPBI(聚2,2'-(间苯基)-5,5'-联苯并咪唑)、30g NMP磁力搅拌,充分溶解后得到PBI溶液S2。将S1、S2均匀混合搅拌、搅拌功率为50W,搅拌时间为6h,得到铸膜液S3。
Step 3:将铸膜液倒入带凹槽的玻璃板中,80℃真空干燥24h,随后120℃真空干燥10h,得到基膜。最后将基膜浸渍在磷酸中,磷酸浓度为85%,浸渍温度为80℃,浸渍时间为20h,得到复合膜。
实施例2
Step 1:称取15g双氰胺,充分研磨后置于坩埚中,随后放在管式炉中煅烧,从室温加热到550℃,升温速率为5℃min-1,空气气氛,升温达到设定温度后,保持4h,随炉降温,将其转移到研钵中仔细研磨成粉末,再分别用1M盐酸溶液清洗1.5h、去离子水清洗清洗2h,所得固体于60℃烘箱中干燥。再将所得固体与0.25g硝酸铈混合,加入50g去离子水,磁力搅拌1h,得到悬浊液。随后向悬浊液中加入1M KOH溶液,调节溶液PH值为13,磁力搅拌2h,离心得到固体沉淀。用大量去离子水清洗,直至溶液PH为中性。最后在烘箱中将物料完全干燥,250℃空气氛围下煅烧2h,得到CeO2@C3N4复合物。
Step 2:称取2.5mg CeO2@C3N4复合物,量取10ml NMP,超声功率为100W,超声4h,得到分散液S1。称取0.27g mPBI(聚2,2'-(间苯基)-5,5'-联苯并咪唑)、30g NMP磁力搅拌,充分溶解后得到PBI溶液S2。将S1、S2均匀混合搅拌、搅拌功率为50W,搅拌时间为6h,得到铸膜液S3。
Step 3:将铸膜液倒入带凹槽的玻璃板中,80℃真空干燥24h,随后120℃真空干燥10h,得到基膜。最后将基膜浸渍在磷酸中,磷酸浓度为85%,浸渍温度为80℃,浸渍时间为20h,得到复合膜。
对比例1
按照实施例1的方法制备复合型高温质子交换膜,双氰胺煅烧产物不以盐酸洗涤。
Step 1:称取15g双氰胺,充分研磨后置于坩埚中,随后放在管式炉中煅烧,从室温加热到550℃,升温速率为5℃min-1,空气气氛,升温达到设定温度后,保持4h,随炉降温,将其转移到研钵中仔细研磨成粉末,再将所得固体与0.2g硝酸铈混合,加入50g去离子水,磁力搅拌1h,得到悬浊液。随后向悬浊液中加入1M KOH溶液,调节溶液PH值为13,磁力搅拌2h,离心得到固体沉淀。用大量去离子水清洗,直至溶液PH为中性。最后在烘箱中将物料完全干燥,250℃空气氛围下煅烧2h,得到CeO2@C3N4复合物。
Step 2:称取0.12mgCeO2@C3N4复合物,量取10ml NMP,超声功率为100W,超声4h,得到分散液S1。称取0.27gmPBI(聚2,2'-(间苯基)-5,5'-联苯并咪唑)、30g NMP磁力搅拌,充分溶解后得到PBI溶液S2。将S1、S2均匀混合搅拌、搅拌功率为50W,搅拌时间为6h,得到铸膜液S3。
Step 3:将铸膜液倒入带凹槽的玻璃板中,80℃真空干燥24h,随后120℃真空干燥10h,得到基膜。最后将基膜浸渍在磷酸中,磷酸浓度为85%,浸渍温度为80℃,浸渍时间为20h,得到复合膜。
对比例2
以聚苯并咪唑和纳米片状C3N4为原料制备复合型高温质子交换膜。
Step 1:称取15g双氰胺,充分研磨后置于坩埚中,随后放在管式炉中煅烧,从室温加热到550℃,升温速率为5℃min-1,空气气氛,升温达到设定温度后,保持4h,随炉降温,将其转移到研钵中仔细研磨成粉末,再分别用1M盐酸溶液清洗1.5h、去离子水清洗清洗2h,所得固体于60℃烘箱中干燥。得到C3N4纳米片。
Step 2:称取0.12mgC3N4纳米片,量取10ml NMP,超声功率为100W,超声4h,得到分散液S1。称取0.27gmPBI(聚2,2'-(间苯基)-5,5'-联苯并咪唑)、30g NMP磁力搅拌,充分溶解后得到PBI溶液S2。将S1、S2均匀混合搅拌、搅拌功率为50W,搅拌时间为6h,得到铸膜液S3。
Step 3:将铸膜液倒入带凹槽的玻璃板中,80℃真空干燥24h,随后120℃真空干燥10h,得到基膜。最后将基膜浸渍在磷酸中,磷酸浓度为85%,浸渍温度为80℃,浸渍时间为20h,得到复合膜。
对比例3
以聚苯并咪唑和纳米片状CeO2为原料制备复合型高温质子交换膜。
Step 1:称取0.2g硝酸铈,加入10g去离子水,磁力搅拌1h,得到悬浊液。随后向悬浊液中加入1M KOH溶液,调节溶液PH值为13,磁力搅拌2h,离心得到固体沉淀。用大量去离子水清洗,直至溶液PH为中性。最后在烘箱中将物料完全干燥,250℃空气氛围下煅烧2h,得到CeO2纳米颗粒。
Step 2:称取0.12mgCeO2纳米颗粒,量取10ml NMP,超声功率为100W,超声4h,得到分散液S1。称取0.27gmPBI(聚2,2'-(间苯基)-5,5'-联苯并咪唑)、30g NMP磁力搅拌,充分溶解后得到PBI溶液S2。将S1、S2均匀混合搅拌、搅拌功率为50W,搅拌时间为6h,得到铸膜液S3。
Step 3:将铸膜液倒入带凹槽的玻璃板中,80℃真空干燥24h,随后120℃真空干燥10h,得到基膜。最后将基膜浸渍在磷酸中,磷酸浓度为85%,浸渍温度为80℃,浸渍时间为20h,得到复合膜。
对比例4
按照实施例1的方法制备复合型高温质子交换膜,CeO2过量掺杂。
Step 1:称取15g双氰胺,充分研磨后置于坩埚中,随后放在管式炉中煅烧,从室温加热到550℃,升温速率为5℃min-1,空气气氛,升温达到设定温度后,保持4h,随炉降温,将其转移到研钵中仔细研磨成粉末,再分别用1M盐酸溶液清洗1.5h、去离子水清洗清洗2h,所得固体于60℃烘箱中干燥。再将所得固体与2.0g硝酸铈混合,加入50g去离子水,磁力搅拌1h,得到悬浊液。随后向悬浊液中加入1M KOH溶液,调节溶液PH值为13,磁力搅拌2h,离心得到固体沉淀。用大量去离子水清洗,直至溶液PH为中性。最后在烘箱中将物料完全干燥,250℃空气氛围下煅烧2h,得到CeO2@C3N4复合物。
Step 2:称取0.12mgCeO2@C3N4复合物,量取10ml NMP,超声功率为100W,超声4h,得到分散液S1。称取0.27gm PBI(聚2,2'-(间苯基)-5,5'-联苯并咪唑)、30g NMP磁力搅拌,充分溶解后得到PBI溶液S2。将S1、S2均匀混合搅拌、搅拌功率为50W,搅拌时间为6h,得到铸膜液S3。
Step 3:将铸膜液倒入带凹槽的玻璃板中,80℃真空干燥24h,随后120℃真空干燥10h,得到基膜。最后将基膜浸渍在磷酸中,磷酸浓度为85%,浸渍温度为80℃,浸渍时间为20h,得到复合膜。
对比例5
Step 1:称取15g双氰胺,充分研磨后置于坩埚中,随后放在管式炉中煅烧,从室温加热到550℃,升温速率为5℃min-1,空气气氛,升温达到设定温度后,保持4h,随炉降温,将其转移到研钵中仔细研磨成粉末,再分别用1M盐酸溶液清洗1.5h、去离子水清洗清洗2h,所得固体于60℃烘箱中干燥。
Step 2:称取2.0g硝酸铈,加入10g去离子水中,磁力搅拌1h,得到悬浊液。随后向悬浊液中加入1M KOH溶液,调节溶液PH值为13,磁力搅拌2h,离心得到固体沉淀。用大量去离子水清洗,直至溶液PH为中性。最后在烘箱中将物料完全干燥,250℃空气氛围下煅烧2h,得到CeO2纳米颗粒。
Step3:称取0.10mg C3N4,0.02mgCeO2,量取10ml NMP,超声功率为100W,超声4h,得到分散液S1。称取0.27gmPBI(聚2,2'-(间苯基)-5,5'-联苯并咪唑)、30g NMP磁力搅拌,充分溶解后得到PBI溶液S2。将S1、S2均匀混合搅拌、搅拌功率为50W,搅拌时间为6h,得到铸膜液S3。
Step4:将铸膜液倒入带凹槽的玻璃板中,80℃真空干燥24h,随后120℃真空干燥10h,得到基膜。最后将基膜浸渍在磷酸中,磷酸浓度为85%,浸渍温度为80℃,浸渍时间为20h,得到复合膜。
将实施例与对比例的复合膜进行扫描电镜测试,结果如图1所示,由图1可以看出,实施例1中CeO2@C3N4复合物中,CeO2含量适中,在C3N4表面分布较均匀,可以在不降低电导率和拉伸强度的前提下,提高对自由基的耐受性。
将实施例1与对比例的复合膜进行电导率和拉伸强度的测试,结果如表1所示。由表1可以看出本发明复合膜的电导率及拉伸强度均有提高,且效果均优于对比例1~对比例5。
表1
将实施例1与对比例1-5的未浸泡磷酸之前的PBI/CeO2@C3N4复合膜浸入Fenton试剂中进行耐久性测试,结果如表2所示。
表2
从表中可以看出,对比例1由于未加盐酸处理C3N4,导致C3N4出现较多团聚,CeO2也出现较多团聚,进而使得CeO2@C3N4复合物没有起到明显的电导率、拉伸强度的提升,对耐久性的提升效果也有限。因此,加盐酸处理C3N4的操作是必要的;对比例2仅掺杂盐酸处理过的C3N4,C3N4具有较多的层状结构,可以较为显著地提高复合膜的电导率、拉伸强度。但是由于没有自由基淬灭剂CeO2的存在,复合膜的耐久性较差;对比例3仅掺杂CeO2的,但CeO2本身不导质子,也不能传递应力,因此该复合膜质子电导率和拉伸强度反而会下降;对比例4中CeO2过量,会掩盖部分C3N4与磷酸作用的活性位点,降低了C3N4与磷酸、PBI树脂与磷酸的接触面积,导致对质子电导率和拉伸强度提升效果十分有限。对比例5中分别添加CeO2、C3N4这两种物质,使得二者没有良好的相互作用,无法在同一个位点同时实现自由基的淬灭和磷酸的吸附锚固。综上所述,实施例1具有最好的实施效果。
对于任何熟悉本领域的技术人员而言,在不脱离本发明技术方案范围情况下,都可利用上述揭示的技术内容对本发明技术方案作出许多可能的变动和修饰,或修改为等同变化的等效实施例。因此,凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所做的任何简单修改、等同变化及修饰,均应仍属于本发明技术方案保护的范围内。
Claims (10)
1.一种复合型高温质子交换膜,其特征在于,其原料包括聚苯并咪唑、复合物A@B和磷酸,其中A为具有自由基淬灭功能的纳米颗粒;B为具有纳米片状结构C3N4;所述复合物A@B的质量分数为0.05-2wt.%,复合物A@B中A与B的质量比为1:1~1:20;所述复合物A@B为A负载在B上;所述纳米片B的厚度为4-10nm。
2.根据权利要求1所述的一种复合型高温质子交换膜,其特征在于,所述复合物A@B中纳米颗粒A的直径为2-10 nm。
3.根据权利要求1所述的一种复合型高温质子交换膜,其特征在于,所述聚苯并咪唑的种类为:mPBI(聚2,2'-(间苯基)-5, 5' -联苯并咪唑)、ABPBI(聚(2,5苯并咪唑))、OPBI(聚2,2'-(对二苯醚基)-5,5'-联苯并咪唑)、带磺酸基侧链的PBI、带膦酸基侧链的PBI、超支化PBI的一种或多种组合;
所述A为MnO2、Mn2O3、Fe3O4、TiO2、CeO2中的一种或多种。
4.根据权利要求1所述的一种复合型高温质子交换膜,其特征在于,所述复合物A@B为纳米颗粒的CeO2负载在纳米片状的C3N4上。
5.根据权利要求1所述的一种复合型高温质子交换膜,其特征在于,所述复合物A@B的制备方法为:
(1)双氰胺研磨后煅烧,煅烧后研磨成粉末,分别用0.25-1.5M盐酸溶液清洗0.5-3 h、去离子水清洗0.5-2 h,所得固体干燥备用;
(2)步骤(1)制得的固体与具有自由基淬灭功能的纳米颗粒的前驱体混合,制得悬浊液;向悬浊液中加入0.5-2.5M KOH溶液,使溶液PH值为12-14,搅拌离心得到固体沉淀,用水清洗至中性,烘干后煅烧得到A@B复合物。
6.根据权利要求5所述的一种复合型高温质子交换膜,其特征在于,所述步骤(1)中双氰胺与具有自由基淬灭功能的纳米颗粒的前驱体的质量比为15:1-5:1;所述煅烧条件为:从室温加热到500-600℃,升温速率为3-8 ℃ min-1,空气气氛,升温达到设定温度后,保持3-6h;所述干燥的温度为60℃;所述步骤(2)中煅烧条件为:250℃空气氛围下煅烧2h。
7.一种如权利要求1所述的复合型高温质子交换膜的制备方法,其特征在于,所述方法包括以下步骤:
(1)以强极性非质子溶剂超声分散A@B复合物,超声一段时间后制得分散液S1;
(2)将聚苯并咪唑(PBI)溶于强极性非质子溶剂,搅拌加热后得到PBI溶液S2;
(3)将S1、S2混合后得到铸膜液S3,S3浇铸在带凹槽的平板玻璃上,干燥后将膜浸泡磷酸中即得。
8.根据权利要求7所述的复合型高温质子交换膜的制备方法,其特征在于,所述步骤(1)中A@B复合物在分散液S1中的质量浓度为0.05-2mg/10ml;所述步骤(2)中聚苯并咪唑在溶液S2中的质量分数为0.8-5wt.%。
9.根据权利要求8所述的复合型高温质子交换膜的制备方法,其特征在于,所述步骤(1)和(2)中的非质子溶剂独立的为N,N-二甲基甲酰胺(DMF)、N, N-二甲基乙酰胺(DMAc)、N-甲基-2吡咯烷酮(NMP)之中的一种或二种以上;
所述步骤(1)中超声功率为50-300 W,超声时间为0.5-6 h;所述步骤(3)中混合方式为磁力搅拌,搅拌功率为50-100 W,搅拌时间为1-12h;
所述聚苯并咪唑膜浸渍磷酸浓度为50-85%,浸渍温度为50-150 ℃,浸渍时间为6-24h。
10.权利要求1所述的复合型高温质子交换膜在燃料电池中的应用。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010969077.5A CN112086672B (zh) | 2020-09-15 | 2020-09-15 | 一种燃料电池用复合型高温质子交换膜及其制备方法和应用 |
US18/245,393 US20240030474A1 (en) | 2020-09-15 | 2021-08-17 | Composite high-temperature proton exchange membrane for fuel cell, preparation method therefor and use thereof |
PCT/CN2021/112975 WO2022057549A1 (zh) | 2020-09-15 | 2021-08-17 | 一种燃料电池用复合型高温质子交换膜及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010969077.5A CN112086672B (zh) | 2020-09-15 | 2020-09-15 | 一种燃料电池用复合型高温质子交换膜及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112086672A CN112086672A (zh) | 2020-12-15 |
CN112086672B true CN112086672B (zh) | 2021-12-07 |
Family
ID=73737901
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010969077.5A Active CN112086672B (zh) | 2020-09-15 | 2020-09-15 | 一种燃料电池用复合型高温质子交换膜及其制备方法和应用 |
Country Status (3)
Country | Link |
---|---|
US (1) | US20240030474A1 (zh) |
CN (1) | CN112086672B (zh) |
WO (1) | WO2022057549A1 (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115020771B (zh) * | 2022-05-07 | 2024-03-15 | 中国地质大学(武汉) | 一种基于hbm共混改性pbi质子交换膜及其制备方法和应用 |
CN115084608B (zh) * | 2022-06-20 | 2024-05-17 | 中国科学技术大学 | 一种抗氧化型质子交换膜、其制备方法及质子交换膜燃料电池 |
CN114874475B (zh) * | 2022-07-11 | 2022-10-04 | 佛山市清极能源科技有限公司 | 一种基于中空聚多巴胺的自增湿质子交换膜及其制备方法与应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106336518A (zh) * | 2015-07-06 | 2017-01-18 | 中国科学院大连化学物理研究所 | 一种聚苯并咪唑/自由基淬灭剂复合膜的制备方法 |
CN108091891A (zh) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | 碱性阴离子交换膜燃料电池阳极纳米催化剂及制备和应用 |
CN109794277A (zh) * | 2019-01-30 | 2019-05-24 | 扬州工业职业技术学院 | 一种二氧化铈/石墨相氮化碳复合材料及其在光催化中的应用 |
CN110444795A (zh) * | 2019-08-27 | 2019-11-12 | 中国科学院化学研究所 | 一种带有纳米片层结构的多孔质子交换复合膜的制备方法 |
CN111342095A (zh) * | 2018-12-18 | 2020-06-26 | 中国科学院青岛生物能源与过程研究所 | 一种高温燃料电池质子交换膜及其制备方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104617323B (zh) * | 2015-01-28 | 2017-01-25 | 大连理工大学 | 一种产电与降解污染物的非光催化与光催化燃料电池系统 |
CN107808969B (zh) * | 2017-09-27 | 2020-11-20 | 广西大学 | 一种高温质子交换膜的制备方法 |
CN108772094A (zh) * | 2018-07-12 | 2018-11-09 | 重庆交通大学 | 一种氮化碳量子点/二氧化钛溶胶及其制备方法 |
CN111244513B (zh) * | 2018-11-28 | 2021-04-02 | 中国科学院大连化学物理研究所 | 一种高温燃料电池质子交换膜及其制备方法与应用 |
-
2020
- 2020-09-15 CN CN202010969077.5A patent/CN112086672B/zh active Active
-
2021
- 2021-08-17 US US18/245,393 patent/US20240030474A1/en active Pending
- 2021-08-17 WO PCT/CN2021/112975 patent/WO2022057549A1/zh active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106336518A (zh) * | 2015-07-06 | 2017-01-18 | 中国科学院大连化学物理研究所 | 一种聚苯并咪唑/自由基淬灭剂复合膜的制备方法 |
CN108091891A (zh) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | 碱性阴离子交换膜燃料电池阳极纳米催化剂及制备和应用 |
CN111342095A (zh) * | 2018-12-18 | 2020-06-26 | 中国科学院青岛生物能源与过程研究所 | 一种高温燃料电池质子交换膜及其制备方法 |
CN109794277A (zh) * | 2019-01-30 | 2019-05-24 | 扬州工业职业技术学院 | 一种二氧化铈/石墨相氮化碳复合材料及其在光催化中的应用 |
CN110444795A (zh) * | 2019-08-27 | 2019-11-12 | 中国科学院化学研究所 | 一种带有纳米片层结构的多孔质子交换复合膜的制备方法 |
Non-Patent Citations (7)
Title |
---|
A novel Ir/CeO2–C nanoparticle electrocatalyst for the hydrogen oxidation reaction of alkaline anion exchange membrane fuel cells;Qin,Bowen等;《RSC Advances》;20170620;第7卷(第50期);第31574-31581页 * |
Degradation reduction of polybenzimidazole membrane blended with CeO2 as a regenerative free radical scavenger;Hao,Jinkai等;《Journal of Membrane Science》;20160909;第522卷;第23-30页 * |
Graphitic Carbon Nitride for Electrochemical Energy Conversion and Storage;Niu, Wenhan等;《ACS ENERGY LETTERS》;20181015;第3卷(第11期);第2796-2815页 * |
Immobilized phosphotungstic acid for the construction of proton exchange nanocomposite membranes with excellent stability and fuel cell performance;Yue,Liu等;《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》;20200516;第45卷(第35期);第17782-17794页 * |
Improved performance of quaternized poly(arylene ether ketone)s/graphitic carbon nitride nanosheets composite anion exchange membrane for fuel cell applications;Lu, Yao等;《APPLIED SURFACE SCIENCE 》;20191020;第503卷;文献号144071 * |
Simultaneously enhancing ionic conduction and mechanical strength of poly (ether sulfones)-poly(vinyl pyrrolidone) membrane by introducing graphitic carbon nitride nanosheets for high temperature proton exchange membrane fuel cell application;Bai, Huijuan等;《JOURNAL OF MEMBRANE SCIENCE》;20180427;第558卷;第26-33页 * |
Titanium oxide/graphitic carbon nitride nanocomposites as fillers for enhancing the performance of SPAES membranes for fuel cells;Ingabire,Providence Buregeya等;《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》;20200811;第91卷;第213-222页 * |
Also Published As
Publication number | Publication date |
---|---|
CN112086672A (zh) | 2020-12-15 |
US20240030474A1 (en) | 2024-01-25 |
WO2022057549A1 (zh) | 2022-03-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112086672B (zh) | 一种燃料电池用复合型高温质子交换膜及其制备方法和应用 | |
Gong et al. | A new strategy for designing high-performance sulfonated poly (ether ether ketone) polymer electrolyte membranes using inorganic proton conductor-functionalized carbon nanotubes | |
Salarizadeh et al. | Enhancing the performance of SPEEK polymer electrolyte membranes using functionalized TiO 2 nanoparticles with proton hopping sites | |
JP5109130B2 (ja) | プロトン伝導性ハイブリッド材料及びそれを用いた燃料電池用触媒層 | |
Salarizadeh et al. | Fabrication and physico-chemical properties of iron titanate nanoparticles based sulfonated poly (ether ether ketone) membrane for proton exchange membrane fuel cell application | |
Salarizadeh et al. | Influence of amine-functionalized iron titanate as filler for improving conductivity and electrochemical properties of SPEEK nanocomposite membranes | |
Pu et al. | Novel branched sulfonated polyimide/molybdenum disulfide nanosheets composite membrane for vanadium redox flow battery application | |
WO2011044778A1 (zh) | 芳香族聚合物离子交换膜及其复合膜在酸性电解液液流储能电池中的应用 | |
US10205194B2 (en) | Highly ion-conductive nano-engineered porous electrolytic composite membrane for alkaline electrochemical energy systems | |
Wang et al. | Anatase titania coated CNTs and sodium lignin sulfonate doped chitosan proton exchange membrane for DMFC application | |
CN109775762A (zh) | 一种空心分等级结构的Fe2O3及Fe2O3/CNT复合材料的制备方法 | |
Zhao et al. | Effect of annealing temperature and element composition of titanium dioxide/graphene/hemin catalysts for oxygen reduction reaction | |
CN112126946B (zh) | 一种酸碱水电解用复合膜及其制备方法和应用 | |
CN106009017A (zh) | 一种支化磺化聚酰亚胺/二维层状材料复合质子导电膜的制备方法 | |
CN116742082A (zh) | 一种磁性纳米颗粒负载磷钨酸-磺化聚醚醚酮复合质子交换膜的制备方法 | |
CN112086673B (zh) | 一种燃料电池用复合型高温质子交换膜及其制备方法 | |
CN101338072B (zh) | 一种有机/无机复合增强型非水质子导电膜及其制备方法 | |
Shi et al. | Ultra-robust, highly proton-conductive polymer carbon dot membranes through bioinspired complexation | |
Gikunoo et al. | Synthesis and characterization of highly durable hydrocarbon-based composite membrane for zinc-bromine redox flow battery | |
Wang et al. | Composite poly (ethylene oxide)-based solid electrolyte with consecutive and fast ion transport channels constructed by upper-dimensional MIL-53 (Al) nanofibers | |
CN113979426A (zh) | 一种磷酸接枝纳米洋葱碳及其制备方法和应用 | |
CN114031870A (zh) | 一种质子交换膜及其制备方法和应用 | |
CN106744849A (zh) | 聚苯并咪唑(pbi)类高分子制备三维石墨烯的方法 | |
CN113120955B (zh) | 接枝磺化丁基二氧化钛纳米管的制备方法 | |
CN114373970B (zh) | 高质子传导率、高耐久性质子交换膜及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |