CN116505043A - Sulfonated polybenzimidazole gel state wide-temperature-range proton exchange membrane with flexible alkyl side chain, and preparation method and application thereof - Google Patents
Sulfonated polybenzimidazole gel state wide-temperature-range proton exchange membrane with flexible alkyl side chain, and preparation method and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 129
- 239000004693 Polybenzimidazole Substances 0.000 title claims abstract description 79
- 229920002480 polybenzimidazole Polymers 0.000 title claims abstract description 79
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 53
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 30
- 239000000446 fuel Substances 0.000 claims abstract description 20
- 150000008053 sultones Chemical group 0.000 claims abstract description 16
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 claims description 8
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 230000036571 hydration Effects 0.000 claims description 8
- 238000006703 hydration reaction Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000007790 scraping Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ANUAIBBBDSEVKN-UHFFFAOYSA-N benzene-1,2,4,5-tetramine Chemical compound NC1=CC(N)=C(N)C=C1N ANUAIBBBDSEVKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 238000003980 solgel method Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012863 analytical testing Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- -1 4-butyl Chemical group 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/18—Polybenzimidazoles
-
- 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
-
- 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
-
- 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
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Conductive Materials (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a sulfonated polybenzimidazole gel state wide-temperature-range proton exchange membrane with a flexible alkyl side chain, and a preparation method and application thereof, wherein the proton membrane is prepared by a polyphosphoric acid sol-gel method and sultone ring opening; the gel proton membrane prepared by the invention has the ultra-high phosphoric acid doping level and excellent proton conduction characteristic and stability (0.069S/cm@25 ℃, 0.162S/cm@80 ℃ and 0.358S/cm@200 ℃) under the wide service temperature range, is applied to a fuel cell, shows good output power, cold starting capability and wide temperature range operation flexibility, and has application prospect in the field of proton exchange membrane fuel cells.
Description
Technical Field
The invention relates to the field of proton exchange membrane fuel cells, in particular to a gel state proton exchange membrane material, and particularly relates to a sulfonated polybenzimidazole gel state wide-temperature-range (25-240 ℃) proton exchange membrane with a flexible alkyl side chain, and a preparation method and application thereof.
Background
The fuel cell is an electrochemical reaction device for directly converting chemical energy of fuel into electric energy, and is considered as one of the most promising clean energy technologies at present due to the advantages of high energy conversion efficiency, low carbon emission and the like. Among the various types of fuel cells, proton Exchange Membrane Fuel Cells (PEMFCs) have been widely studied and applied due to their advantages of high output power, fast response, small volume, and the like. Proton Exchange Membranes (PEM) are the key core material of PEMFCs, playing a role in proton transport, fuel and air barrier, and directly determining the performance and life of the cell.
Proton exchange membranes can be classified into low temperature (< 80 ℃) and high temperature (120-200 ℃) depending on the service temperature. Of the low temperature proton membranes, the most representative are perfluorosulfonic acid type proton exchange membranes (e.g., nafion). Since its proton transport is water dependent, it does not exhibit reasonable proton conduction properties under either high temperature (> 80 ℃) or low humidity conditions. In addition, the proton exchange membrane has the problems of low glass transition temperature, complex preparation process, high cost and the like, and limits the further development and application of the proton exchange membrane (chem. Soc. Rev,2021,50 (2): 1138-1187). In contrast, the most widely studied of high temperature proton exchange membranes is the phosphate doped polybenzimidazole (PA/PBI) proton exchange membrane capable of operating in a non-aqueous environment. PEMFCs based on such membranes offer rapid reaction kinetics, simplified water/thermal management systems and diverse fuel sources, while increasing catalyst tolerance to impurity gases, and exhibit great market potential and application prospects (Nature Materials,2021,20 (3): 370-377).
The traditional method for preparing the PA/PBI proton exchange membrane comprises the steps of polymerization, polymer dissolution and filtration, membrane casting, drying, phosphoric acid doping and the like. The method is time-consuming and labor-consuming, requires a large amount of organic solvents, is difficult to process, and has a relatively single synthesizable PBI structure. More importantly, the prepared membrane is of a compact structure, generally has lower phosphoric acid doping level and proton conductivity, and has serious phosphoric acid loss. When the acid doping level approaches a high peak, the mechanical properties of the film drop drastically due to the plasticizing effect, and thus cannot be used normally in battery devices (Journal of Polymer Science Part B: polymer Physics,2014.52 (1): 26-35). Therefore, the problem that the proton conductivity and the mechanical property are difficult to be cooperated and compatible (trade-off) and the doping content of phosphoric acid is limited causes the development and the application of the high-temperature proton exchange membrane to be in a bottleneck. In addition, the low temperature operation and cold start capability of fuel cells are still faced with a serious challenge due to the low degree of phosphate dissociation, limited proton transfer activity and poor conductivity of such membrane materials at low temperatures. Therefore, developing a high-temperature proton exchange membrane material with higher proton conductivity and stability at low temperature is important for solving the low-temperature frequency start, widening the service temperature window and meeting the commercial operation requirement.
Disclosure of Invention
In order to overcome the defects of the existing proton exchange membrane, the invention provides a sulfonated polybenzimidazole gel state wide-temperature-range proton exchange membrane with an ultrahigh phosphoric acid doping level and a flexible alkyl side chain with excellent proton conduction characteristics in a wide temperature and humidity range, a preparation method thereof and application thereof in a fuel cell.
The conception of the invention is as follows: the sulfonated polybenzimidazole gel state wide temperature range proton exchange membrane with flexible alkyl side chains is prepared by adopting a polyphosphoric acid sol-gel method and sultone ring-opening reaction. The proton membrane prepared by the invention widens the operating temperature range, realizes the normal-temperature start of the battery, and has good application prospect in the field of fuel cells.
The technical scheme of the invention is as follows:
a sulfonated polybenzimidazole gel state wide temperature range proton exchange membrane with flexible alkyl side chains is composed of sulfonated polybenzimidazole with flexible alkyl side chains, phosphoric acid and water;
wherein the structural unit of the sulfonated polybenzimidazole with a flexible alkyl side chain is one or more of the following:
the sulfonated polybenzimidazole with flexible alkyl side chains is a homopolymer or a random copolymer, and the weight average molecular weight of the sulfonated polybenzimidazole is 50000-130000; x is the number of carbon atoms in the alkyl side chain, x=3 or 4.
The sulfonated polybenzimidazole gel state wide temperature range proton exchange membrane with the flexible alkyl side chain has a lamellar porous structure, the pore size of the membrane is 0.3-100 nm, and the thickness of the membrane is 50-600 mu m.
A preparation method of a sulfonated polybenzimidazole gel state wide temperature range proton exchange membrane with a flexible alkyl side chain comprises the following steps:
s1, in a nitrogen environment, carrying out condensation reaction on an aromatic tetraamine monomer and a dicarboxylic acid monomer in polyphosphoric acid at 120-250 ℃ for 5-50 h to obtain a polybenzimidazole polymer solution;
the aromatic tetraamine monomer is selected from one or a mixture of two of 3,3' -diaminobenzidine and 1,2,4, 5-tetraaminobenzene in any proportion;
the dicarboxylic acid monomer is selected from one or more than two of isophthalic acid, terephthalic acid, 2, 5-dihydroxyterephthalic acid and 4,4' -dicarboxydiphenyl ether in any proportion;
preferably, the molar ratio of aromatic tetraamine monomer to dicarboxylic acid monomer is 1:1, a step of;
polyphosphoric acid is used as a reaction solvent, and after the aromatic tetraamine monomer and the dicarboxylic acid monomer are mixed in the polyphosphoric acid, the total mass fraction of the monomers is 1-15 wt%;
s2, scraping the polybenzimidazole polymer solution obtained in the step S1 on a glass substrate, cooling to room temperature, and completing the phase conversion from the solution to a gel state membrane by utilizing the difference of solubility of polybenzimidazole in polyphosphoric acid and phosphoric acid and the process of hydration of polyphosphoric acid to phosphoric acid to obtain an initial polybenzimidazole gel state proton membrane;
typically the initial polybenzimidazole gel state proton membrane has a phosphoric acid content of 45 to 75wt% and an acid doping level of 15 to 65mol PA/PRU;
s3, soaking the initial polybenzimidazole gel state proton membrane obtained in the S2 into neutral by deionized water (to remove phosphoric acid doped in the membrane to form a layered porous structure), placing the proton membrane in a sultone solution, performing ring-opening reaction for 12-24 hours at 25-80 ℃, and then washing the proton membrane by deionized water (to remove unreacted sultone) to obtain a modified proton membrane;
preferably, the initial polybenzimidazole gel state proton membrane is soaked in deionized water at room temperature for 3-4 days, and water is changed every 24 hours;
the sultone is taken as a modified monomer and is selected from one or a mixture of two of 1, 3-propane sultone and 1, 4-butane sultone in any proportion; the solvent in the sultone solution is selected from one or more of ethanol, methanol, deionized water, DMAc and DMF; the concentration of the sultone solution is 0.05-0.5 mol/L;
s4, soaking the modified proton membrane obtained in the S3 in a phosphoric acid solution for acid doping to obtain the sulfonated polybenzimidazole gel state wide-temperature-range proton exchange membrane with the flexible alkyl side chain;
preferably the concentration of the phosphoric acid solution is 85wt%; the phosphoric acid solution is used for soaking the modified proton membrane at room temperature for 48-120 h, so as to dope phosphoric acid.
The sulfonated polybenzimidazole gel state wide temperature range proton exchange membrane with the flexible alkyl side chain can be applied to fuel cells, and the specific application method is as follows:
(1) Platinum was supported at 1mg/cm -2 The gas diffusion electrode of (2) and the sulfonated polybenzimidazole gel state proton membrane are prepared into a Membrane Electrode Assembly (MEA) by a high-temperature hot-pressing mode;
(2) Installing the MEA obtained in the step (1) in a fuel cell single cell testing device;
(3) Performing polarization curve test on the fuel cell testing device in the step (2) within the temperature range of 25-240 ℃;
the polarization curve test does not require additional humidification; h used in the test procedure 2 Is 50SCCM (1.5 stoichiometric) O 2 The minimum flow of (2) is 100SCCM (stoichiometric) with no additional pressurization.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation conditions of the polyphosphoric acid sol-gel method and the ring-opening reaction adopted by the invention are mild, the method is simple, the cost is low, the structure and the appearance of the membrane material are easy to control, the uniformity is good, and the mass production is easy.
(2) The gel state proton exchange membrane prepared by the invention has lamellar porous structure, is beneficial to rapid and efficient doping and storage of phosphoric acid, and avoids the problems of low acid content and serious loss of the traditional dense membrane.
(3) The sulfonated polybenzimidazole gel state proton exchange membrane prepared by the invention can provide a proton transmission path with double sites of a sulfonic acid group and an aromatic imidazole skeleton connected by flexible alkyl side chains, has excellent proton conductivity in a wide temperature and humidity range, widens the operating temperature range of a fuel cell to 25-240 ℃, and has good application prospect.
(4) The gel type proton exchange membrane prepared by the invention has high phosphoric acid doping level and proton conductivity, can meet the mechanical strength requirement of device application, and has excellent thermochemical stability (the decomposition temperature is more than 500 ℃ and the glass transition temperature is more than 400 ℃).
(5) The invention widens the variety and application range of membrane materials for proton exchange membrane fuel cell technology.
Drawings
FIG. 1 is an infrared analysis spectrum of proton exchange membrane in comparative example and example.
Fig. 2 is a graph of the microtopography of proton exchange membranes in comparative examples and examples.
Figure 3 is the proton conductivity (no additional humidification) of the proton exchange membrane in the comparative and examples.
Figure 4 is the conductivity stability of the proton exchange membrane at 80 c/40% rh in the comparative and examples.
Figure 5 is the conductivity stability of the proton exchange membrane at 25 c/80% rh in the comparative and examples.
FIG. 6 is a graph showing the polarization of the fuel cell at 25-240℃for the proton exchange membrane of example 4.
Detailed Description
In order that the invention may be understood, a more complete description of the invention will be rendered by reference to the following examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Comparative example 1:
the method comprises the following specific steps:
the conventional type PA/PBI film provided by PBI Performance company was immersed in 85wt% phosphoric acid solution for 168 hours to complete acid doping, thereby preparing the conventional type PA/PBI film.
Analytical testing was performed on the conventional PA/PBI film obtained in comparative example 1:
experimental results: phosphoric acid doping level: 7.73mol PA/PRU.
Proton conductivity (no additional humidification): conductivity at 25 ℃): conductivity at 80℃of 0.015S/cm: conductivity at 200℃at 0.051S/cm: conductivity at 0.096S/cm,240 ℃): 0.070S/cm.
Comparative example 2:
the method comprises the following specific steps:
s1, placing 2.7855g of 3,3' -diaminobenzidine (0.013 mol) and 2.1611g of terephthalic acid (0.013 mol) into a three-port open reaction kettle, adding 160mL of polyphosphoric acid, and controlling the monomer content to be 3wt%; stirring the reaction mixture by using a mechanical stirrer, and reacting for 24 hours at 190 ℃ under the protection of nitrogen flow to obtain a PBI polymer solution;
s2, scraping the obtained polymer solution on a glass substrate, cooling to room temperature, and completing the phase conversion from the solution to a gel state membrane by utilizing the difference of solubility of polybenzimidazole in polyphosphoric acid and phosphoric acid and the process of hydration of polyphosphoric acid to phosphoric acid to obtain an initial polybenzimidazole gel state proton exchange membrane; the blade coating thickness was 254. Mu.m.
Analytical testing of the PA/PBI gel proton membrane obtained in comparative example 2:
experimental results: phosphoric acid doping level: 62.83mol PA/PRU.
Proton conductivity (no additional humidification): conductivity at 25 ℃): conductivity at 80℃of 0.028S/cm: conductivity at 0.112S/cm,200 ℃ C: conductivity at 0.261S/cm,240 ℃): 0.248S/cm.
In addition, the membranes were tested for proton conductivity and stability at 80 ℃/40% rh and 25 ℃/80% rh. The proton conductivity at 80 ℃/40% RH eventually stabilizes at 0.066S/cm; the proton conductivity at 25 ℃/80% RH eventually stabilizes at 0.148S/cm.
Example 1:
the method comprises the following specific steps:
s1, placing 2.7855g of 3,3' -diaminobenzidine (0.013 mol) and 2.1611g of terephthalic acid (0.013 mol) into a three-port open reaction kettle, adding 160mL of polyphosphoric acid, and controlling the monomer content to be 3wt%; stirring the reaction mixture by using a mechanical stirrer, and reacting for 24 hours at 190 ℃ under the protection of nitrogen flow to obtain a PBI polymer solution;
s2, scraping the obtained polymer solution on a glass substrate, cooling to room temperature, and completing the phase conversion from the solution to a gel state membrane by utilizing the difference of solubility of polybenzimidazole in polyphosphoric acid and phosphoric acid and the process of hydration of polyphosphoric acid to phosphoric acid to obtain an initial polybenzimidazole gel state proton exchange membrane; the blade coating thickness is 254 μm;
s3, soaking the obtained membrane with deionized water to remove phosphoric acid contained in the membrane, placing the membrane in a 1, 3-propane sultone ethanol solution with the concentration of 0.05mol/L, reacting for 24 hours at 70 ℃, and then washing the membrane with deionized water for multiple times to remove unreacted sultone modified monomers;
s4, soaking the modified membrane in 85wt% phosphoric acid solution for 48 hours for acid doping to obtain the sulfonated polybenzimidazole gel state wide temperature range proton exchange membrane with flexible alkyl side chains.
Analytical testing of the PA/PBI gel proton membrane obtained in example 1:
experimental results: phosphoric acid doping level: 64.87mol PA/PRU.
Proton conductivity (no additional humidification): conductivity at 25 ℃): conductivity at 80℃of 0.045S/cm: conductivity at 0.139S/cm,200 ℃ C: 0.309S/cm, conductivity at 200 ℃): 0.289S/cm.
Example 2:
the method comprises the following specific steps:
s1, placing 2.7855g of 3,3' -diaminobenzidine (0.013 mol) and 2.1611g of terephthalic acid (0.013 mol) into a three-port open reaction kettle, adding 160mL of polyphosphoric acid, and controlling the monomer content to be 3wt%; stirring the reaction mixture by using a mechanical stirrer, and reacting for 32 hours at 190 ℃ under the protection of nitrogen flow to obtain a PBI polymer solution;
s2, scraping the obtained polymer solution on a glass substrate, cooling to room temperature, and completing the phase conversion from the solution to a gel state membrane by utilizing the difference of solubility of polybenzimidazole in polyphosphoric acid and phosphoric acid and the process of hydration of polyphosphoric acid to phosphoric acid to obtain an initial polybenzimidazole gel state proton exchange membrane; the blade coating thickness is 254 μm;
s3, soaking the obtained membrane with deionized water to remove phosphoric acid contained in the membrane, placing the membrane in a 1, 3-propane sultone ethanol solution with the concentration of 0.1mol/L, reacting for 24 hours at 70 ℃, and then washing the membrane with deionized water for multiple times to remove unreacted sultone modified monomers;
s4, soaking the modified membrane in 85wt% phosphoric acid solution for 48 hours for acid doping to obtain the sulfonated polybenzimidazole gel state wide temperature range proton exchange membrane with flexible alkyl side chains.
Analytical testing of the PA/PBI gel proton membrane obtained in example 2:
experimental results: phosphoric acid doping level: 65.38mol PA/PRU.
Proton conductivity (no additional humidification): conductivity at 25 ℃): conductivity at 80℃of 0.055S/cm: conductivity at 0.128S/cm,200 ℃ C: conductivity at 0.310S/cm,240 ℃ C: 0.312S/cm.
Example 3:
the method comprises the following specific steps:
s1, placing 2.7855g of 3,3' -diaminobenzidine (0.013 mol) and 2.1611g of terephthalic acid (0.013 mol) into a three-port open reaction kettle, adding 160mL of polyphosphoric acid, and controlling the monomer content to be 3wt%; stirring the reaction mixture by using a mechanical stirrer, and reacting for 32 hours at 190 ℃ under the protection of nitrogen flow to obtain a PBI polymer solution;
s2, scraping the obtained polymer solution on a glass substrate, cooling to room temperature, and completing the phase conversion from the solution to a gel state membrane by utilizing the difference of solubility of polybenzimidazole in polyphosphoric acid and phosphoric acid and the process of hydration of polyphosphoric acid to phosphoric acid to obtain an initial polybenzimidazole gel state proton exchange membrane; the blade coating thickness is 254 μm;
s3, soaking the obtained membrane with deionized water to remove phosphoric acid contained in the membrane, placing the membrane in a 1, 3-propane sultone ethanol solution with the concentration of 0.2mol/L, reacting for 24 hours at 70 ℃, and then washing the membrane with deionized water for multiple times to remove unreacted sultone modified monomers;
s4, soaking the modified membrane in 85wt% phosphoric acid solution for 48 hours for acid doping to obtain the sulfonated polybenzimidazole gel state wide temperature range proton exchange membrane with flexible alkyl side chains.
Analytical testing of the PA/PBI gel proton membrane obtained in example 3:
experimental results: phosphoric acid doping level: 64.35mol PA/PRU.
Proton conductivity (no additional humidification): conductivity at 25 ℃): conductivity at 80℃of 0.066S/cm: conductivity at 0.155S/cm,200 ℃ C: conductivity at 0.347S/cm,240 ℃): 0.336S/cm.
Example 4:
the method comprises the following specific steps:
s1, placing 2.7855g of 3,3' -diaminobenzidine (0.013 mol) and 2.1611g of terephthalic acid (0.013 mol) into a three-port open reaction kettle, adding 160mL of polyphosphoric acid, and controlling the monomer content to be 3wt%; stirring the reaction mixture by using a mechanical stirrer, and reacting for 28 hours at 190 ℃ under the protection of nitrogen flow to obtain a PBI polymer solution;
s2, scraping the obtained polymer solution on a glass substrate, cooling to room temperature, and completing the phase conversion from the solution to a gel state membrane by utilizing the difference of solubility of polybenzimidazole in polyphosphoric acid and phosphoric acid and the process of hydration of polyphosphoric acid to phosphoric acid to obtain an initial polybenzimidazole gel state proton exchange membrane; the blade coating thickness is 254 μm;
s3, soaking the obtained membrane with deionized water to remove phosphoric acid contained in the membrane, placing the membrane in a 1, 3-propane sultone ethanol solution with the concentration of 0.3mol/L, reacting for 24 hours at 70 ℃, and then washing the membrane with deionized water for multiple times to remove unreacted sultone modified monomers;
s4, soaking the modified membrane in 85wt% phosphoric acid solution for 48 hours for acid doping to obtain the sulfonated polybenzimidazole gel state wide temperature range proton exchange membrane with flexible alkyl side chains.
Analytical testing of the PA/PBI gel proton membrane obtained in example 4:
experimental results: phosphoric acid doping level: 66.47mol PA/PRU.
Proton conductivity (no additional humidification): conductivity at 25 ℃): conductivity at 80℃of 0.069S/cm: conductivity at 0.162S/cm,200 ℃ C: conductivity at 0.358S/cm,240 ℃): 0.339S/cm.
The PA/PBI gel proton membrane obtained in example 4 was mounted in a fuel cell device and subjected to polarization curve test: maximum power density at 25 ℃): 93mW/cm 2 Maximum power density at 80 ℃): 191mW/cm 2 Maximum power density at 160 ℃): 370mW/cm 2 Maximum power density at 220 ℃): 496mW/cm 2 Maximum power density at 240 ℃): 339mW/cm 2 。
In addition, the membranes were tested for proton conductivity and stability at 80 ℃/40% rh and 25 ℃/80% rh. The proton conductivity at 80 ℃/40% RH eventually stabilizes at 0.130S/cm; the proton conductivity at 25℃and 80% RH eventually stabilizes at 0.169S/cm.
Example 5:
the method comprises the following specific steps:
s1, placing 2.7855g of 3,3' -diaminobenzidine (0.013 mol) and 2.1611g of terephthalic acid (0.013 mol) into a three-port open reaction kettle, adding 160mL of polyphosphoric acid, and controlling the monomer content to be 3wt%; stirring the reaction mixture by using a mechanical stirrer, and reacting for 28 hours at 190 ℃ under the protection of nitrogen flow to obtain a PBI polymer solution;
s2, scraping the obtained polymer solution on a glass substrate, cooling to room temperature, and completing the phase conversion from the solution to a gel state membrane by utilizing the difference of solubility of polybenzimidazole in polyphosphoric acid and phosphoric acid and the process of hydration of polyphosphoric acid to phosphoric acid to obtain an initial polybenzimidazole gel state proton exchange membrane; the blade coating thickness is 254 μm;
s3, soaking the obtained membrane with deionized water to remove phosphoric acid contained in the membrane, placing the membrane in a 1, 4-butyl sultone ethanol solution with the concentration of 0.3mol/L, reacting for 24 hours at 70 ℃, and then washing the membrane with deionized water for multiple times to remove unreacted sultone modified monomers;
s4, soaking the modified membrane in 85wt% phosphoric acid solution for 48 hours for acid doping to obtain the sulfonated polybenzimidazole gel state wide temperature range proton exchange membrane with flexible alkyl side chains.
Analytical testing of the PA/PBI gel proton membrane obtained in example 5:
experimental results: phosphoric acid doping level: 63.47mol PA/PRU.
Proton conductivity (no additional humidification): conductivity at 25 ℃): 0.062S/cm, conductivity at 80 ℃): conductivity at 0.143S/cm,200 ℃ C: conductivity at 0.290S/cm,240 ℃): 0.265S/cm.
Table 1 membrane component analysis of proton exchange membranes in comparative examples and examples.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and falls within the scope of the present invention as long as the present invention meets the requirements.
Claims (10)
1. The wide-temperature-range proton exchange membrane with flexible alkyl side chains and in the gel state of the sulfonated polybenzimidazole is characterized by comprising the sulfonated polybenzimidazole with flexible alkyl side chains, phosphoric acid and water;
wherein the structural unit of the sulfonated polybenzimidazole with a flexible alkyl side chain is one or more of the following:
the sulfonated polybenzimidazole with flexible alkyl side chains is a homopolymer or a random copolymer, and the weight average molecular weight of the sulfonated polybenzimidazole is 50000-130000; x is the number of carbon atoms in the alkyl side chain, x=3 or 4.
2. The sulfonated polybenzimidazole gel state wide temperature range proton exchange membrane with flexible alkyl side chains according to claim 1, which has a lamellar porous structure with a pore size of 0.3nm to 100nm and a thickness of 50 μm to 600 μm.
3. The method for preparing a sulfonated polybenzimidazole gel state wide temperature range proton exchange membrane with flexible alkyl side chains according to claim 1, wherein the preparation method comprises the following steps:
s1, in a nitrogen environment, carrying out condensation reaction on an aromatic tetraamine monomer and a dicarboxylic acid monomer in polyphosphoric acid at 120-250 ℃ for 5-50 h to obtain a polybenzimidazole polymer solution;
the aromatic tetraamine monomer is selected from one or a mixture of two of 3,3' -diaminobenzidine and 1,2,4, 5-tetraaminobenzene in any proportion;
the dicarboxylic acid monomer is selected from one or more than two of isophthalic acid, terephthalic acid, 2, 5-dihydroxyterephthalic acid and 4,4' -dicarboxydiphenyl ether in any proportion;
s2, scraping the polybenzimidazole polymer solution obtained in the step S1 on a glass substrate, cooling to room temperature, and completing the phase conversion from the solution to a gel state membrane by utilizing the difference of solubility of polybenzimidazole in polyphosphoric acid and phosphoric acid and the process of hydration of polyphosphoric acid to phosphoric acid to obtain an initial polybenzimidazole gel state proton membrane;
s3, soaking the initial polybenzimidazole gel state proton membrane obtained in the S2 into neutral by deionized water, placing the initial polybenzimidazole gel state proton membrane in a sultone solution, performing ring-opening reaction for 12-24 hours at 25-80 ℃, and then cleaning the initial polybenzimidazole gel state proton membrane by deionized water to obtain a modified proton membrane;
the sultone is selected from one or two of 1, 3-propane sultone and 1, 4-butane sultone in any proportion;
s4, soaking the modified proton membrane obtained in the step S3 in a phosphoric acid solution for acid doping to obtain the sulfonated polybenzimidazole gel state wide-temperature-range proton exchange membrane with the flexible alkyl side chain.
4. The process according to claim 3, wherein in S1, the molar ratio of the aromatic tetraamine monomer to the dicarboxylic acid monomer is 1:1.
5. the process according to claim 3, wherein in S1, the aromatic tetraamine monomer and the dicarboxylic acid monomer are mixed in polyphosphoric acid, and the total mass fraction of the monomers is 1 to 15wt%.
6. The method of claim 3, wherein in S3, the initial polybenzimidazole gel state proton membrane is soaked with deionized water at room temperature for 3-4 days, and water is changed every 24 hours.
7. The preparation method according to claim 3, wherein in S3, the solvent in the sultone solution is one or more selected from ethanol, methanol, deionized water, DMAc, DMF; the concentration of the sultone solution is 0.05-0.5 mol/L.
8. The process according to claim 3, wherein the concentration of the phosphoric acid solution in S4 is 85wt%.
9. The method according to claim 3, wherein in S4, the phosphoric acid solution is used for soaking the modified proton membrane at room temperature for 48-120 hours.
10. Use of a sulfonated polybenzimidazole gel state broad temperature range proton exchange membrane with flexible alkyl side chains according to claim 1 in a fuel cell.
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