CN117276607A - High-temperature proton exchange membrane modified by guanidine salt based on polybenzimidazolyl and preparation method thereof - Google Patents
High-temperature proton exchange membrane modified by guanidine salt based on polybenzimidazolyl and preparation method thereof Download PDFInfo
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- CN117276607A CN117276607A CN202311198899.8A CN202311198899A CN117276607A CN 117276607 A CN117276607 A CN 117276607A CN 202311198899 A CN202311198899 A CN 202311198899A CN 117276607 A CN117276607 A CN 117276607A
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- 239000012528 membrane Substances 0.000 title claims abstract description 61
- 150000002357 guanidines Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 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 abstract description 26
- 241000018242 Obba <basidiomycete fungus> Species 0.000 claims abstract description 22
- 239000000446 fuel Substances 0.000 claims abstract description 12
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 34
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 150000001350 alkyl halides Chemical class 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012456 homogeneous solution Substances 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 claims 2
- XHQZXHMRBXBPEL-UHFFFAOYSA-N eaton reagent Chemical compound CS(O)(=O)=O.O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 XHQZXHMRBXBPEL-UHFFFAOYSA-N 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 101
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 50
- 239000004693 Polybenzimidazole Substances 0.000 abstract description 18
- 229920002480 polybenzimidazole Polymers 0.000 abstract description 18
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 abstract description 4
- -1 halogen alkylated guanidine salt Chemical class 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 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 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 238000009830 intercalation Methods 0.000 abstract description 2
- 230000002687 intercalation Effects 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- 238000012643 polycondensation polymerization Methods 0.000 abstract description 2
- 229920006254 polymer film Polymers 0.000 abstract description 2
- 229920001002 functional polymer Polymers 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- 230000008961 swelling Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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
- H01M8/1016—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]
-
- 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
-
- 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
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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
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
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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
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- 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
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- 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
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- Fuel Cell (AREA)
Abstract
The invention belongs to the field of high-temperature proton exchange membrane fuel cells, and particularly relates to a polybenzimidazole-based guanidine salt modified high-temperature proton exchange membrane and a preparation method thereof. The hydroxyl functional OPBI is obtained by polycondensation polymerization of 3,3 '-Diaminobenzidine (DAB), 4' -dicarboxylic acid diphenyl ether (OBBA) and 2, 5-dihydroxyterephthalic acid (DHTA) at high temperature, and then the proton exchange membrane is obtained by introducing guanidine groups on the basis of the hydroxyl functional polymer. The intercalation of hydroxyl functional groups may provide additional transfer sites for protons. The alkaline group halogen alkylated guanidine salt additionally introduced into the polybenzimidazole can effectively improve the phosphoric acid adsorption capacity of the polymer film. The introduction of guanidine groups can also improve the phosphate retention capacity of the membrane.
Description
Technical Field
The invention belongs to the field of high-temperature proton exchange membrane fuel cells, and particularly relates to a polybenzimidazole-based guanidine salt modified high-temperature proton exchange membrane and a preparation method thereof.
Background
A high temperature proton exchange membrane fuel cell (HT-PEMFC) is a device that directly converts chemical energy in fuel and catalyst into electrical energy in an electrochemical reaction manner without combustion. The fuel of HT-PEMFC is usually low-carbon energy such as hydrogen, and the byproducts are discharged into the environment in the form of water after electrochemical reaction conversion, so that the fuel is a clean energy device which meets the environmental protection requirement, and has very wide development prospect in the fuel cell direction of automobiles and the like.
Proton Exchange Membranes (PEM) are the core component of HT-PEMFCs, which function primarily to selectively pass protons and to isolate anode hydrogen from cathode oxygen. Proton conductivity and mechanical strength properties of the PEM will directly impact the electrochemical performance and service life of the fuel cell, so the PEM is generally required to have higher proton conductivity, lower fuel and oxidant permeability, stable chemical properties and excellent mechanical properties, and lower cost.
The membrane material used at home and abroad is mainly Nafion membrane developed by DuPont in U.S., the Nafion membrane has excellent performances in electrochemical performance, service life and the like, but the development of the Nafion membrane is limited by an expensive and complex water thermal management system, and the dependence of the Nafion membrane on water causes that the Nafion membrane is difficult to be suitable for a high-temperature proton exchange membrane fuel cell with excellent comprehensive performance. Therefore, it has become urgent to develop a PEM having high proton conductivity, high chemical stability, high thermal stability, and low cost.
Polybenzimidazole (PBI) is a very rigid polymer having excellent mechanical strength, chemical stability and thermal stability. The disadvantage is that the PBI has little proton transmission capability, and needs to rely on proton acid (phosphoric acid, hydrochloric acid and the like) to provide the proton transmission capability, however, the adsorption capability of the common PBI to phosphoric acid is limited, in addition, the PBI can generate a plasticization phenomenon after adsorbing the phosphoric acid, and the mechanical strength of the membrane can be greatly reduced. These have all greatly limited the development of PBI in the HT-PEM field. There is an urgent need to develop a polymer exchange membrane having high acid absorption and high stability.
Disclosure of Invention
The invention provides a polybenzimidazole based high-temperature proton exchange membrane and a preparation method thereof. Hydroxy-functionalized OPBI is obtained by polycondensation polymerization of 3,3 '-Diaminobenzidine (DAB), 4' -dicarboxylic acid diphenyl ether (OBBA) and 2, 5-dihydroxyterephthalic acid (DHTA) at high temperature. The intercalation of hydroxyl functional groups may provide additional transfer sites for protons. The alkaline group halogen alkylated guanidine salt additionally introduced into the polybenzimidazole can effectively improve the phosphoric acid adsorption capacity of the polymer film. The introduction of guanidine groups can also improve the phosphate retention capacity of the membrane.
In order to achieve the above object, the present invention adopts the following technical scheme: a high-temperature proton exchange membrane modified by guanidine salt based on polybenzimidazolyl has the following structural formula:
wherein x is an integer value of 1-10, n is the molar ratio of OBBA to DHTA, the value range is 0-1, and 0 and 1 are not taken.
The preparation method of the high-temperature phosphoric acid proton exchange membrane comprises the following steps:
(1) Preparation of hydroxy-functionalized OPBI
Removing residual air in solvent (PPA) by mechanical stirring under nitrogen atmosphere, and sequentially adding DAB, OBBA, DHTA and P 2 O 5 After complete dissolution, the temperature is raised to 140 ℃ for reaction for 3 hours, and polymerization is carried out for 24 hours at 180 ℃. Pouring the polymer solution into deionized water to precipitate solid, adding NaHCO 3 And regulating the pH of the system to be neutral, and oven-drying the solid to obtain the hydroxyl functional OPBI, which is named as OH-OPBI-X. (wherein X is the total mole percent of DHTA between OBBA and DHTA).
Wherein, PPA solvent in preparing polybenzimidazole can also be replaced by Eton reagent (namely mixed solution of methanesulfonic acid and phosphorus pentoxide);
the molar ratio of DAB to (OBBA+DHTA) is 1:1; wherein the molar ratio of OBBA to DHTA is 0-1, but is not 0 and 1, and OBBA+DHTA is 1; p (P) 2 O 5 The dosage of (2) is 3-4 times of the sum of DAB, OBBA, DHTA.
(2) Preparation of guanidine salts
Slowly dropwise adding haloalkane into acetonitrile solution of tetramethyl guanidine (TMG) in ice water bath and nitrogen atmosphere, transferring to room temperature for reaction for 24h after dropwise adding, removing solvent, washing the product with ethyl acetate for 3 times, and removing ethyl acetate to obtain the pentaalkyl guanidine salt.
Wherein the halogen element in the haloalkane comprises fluorine, chlorine, bromine and iodine, the number of the alkyl is 1-10, such as 1, 2-dibromoethane, 1, 3-dibromopropane, 1, 4-dibromobutane and the like;
the molar ratio of the tetramethylguanidine to the haloalkane is 1:1.1;
(3) Grafting and film formation
The OH-OPBI-X polymer prepared in the step (1) is dissolved in dimethyl sulfoxide to form a homogeneous solution (the dissolution temperature is 80 ℃), and the reaction is continued with stirring after the addition of the pentaalkyl guanidine salt for 24 hours. The solution was poured into water, the precipitated solid was washed with water and then dried, and the resulting product was designated TMG/OH-OPBI-X.
The organic solvent that dissolves the OH-OPBI-X polymer may also be: n, N-dimethylformamide or N-methylpyrrolidone.
The molar ratio of the OH-OPBI-X polymer to the pentaalkyl guanidine salt is 1:a, and the value of a is 0.1-2.2.
Dissolving TMG/OH-OPBI-X in dimethyl sulfoxide (dissolution temperature is 80 ℃) to form a homogeneous solution, casting the film solution onto a glass plate, and drying in an oven to obtain the film.
And (3) soaking the dried membrane in 85wt% phosphoric acid for 24 hours at 80 ℃, finishing phosphoric acid doping, taking out the membrane, and wiping off residual phosphoric acid on the surface to obtain the polybenzimidazole phosphoric acid doped proton exchange membrane.
The solvent used in the film formation may be N, N-dimethylformamide, N-methylpyrrolidone, or the like, in addition to dimethyl sulfoxide.
The proton exchange membrane based on polybenzimidazole prepared by the invention can be used for fuel cells.
Compared with the prior art, the invention has the following advantages:
(1) The hydroxyl functional OPBI polymer contains a phenolic hydroxyl structure, can provide an additional transfer site for protons, and is beneficial to proton conduction;
(2) The grafted PBI polymer contains hydrophilic and strong alkaline guanidine groups, which is beneficial to the adsorption of phosphoric acid;
(3) The existence of the strong alkaline guanidine salt group can provide relatively strong acid-base interaction, so that the fixing capacity of phosphoric acid is improved;
(4) The copolymer has simple and efficient synthesis process and is suitable for large-scale preparation.
Description of the drawings:
FIG. 1 is a schematic diagram of the preparation [ BrBuTMG]Br (a), OH-OPBI-10 (b) and TMG/OH-OPBI-10 (c) 1 HNMR diagram.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
120g of PPA is weighed into a three-necked flask, nitrogen is introduced, residual air in the PPA is removed by mechanical stirring, and 1.92g of DAB,2.10g of OBBA,0.18g of DHTA and 12g of P are added 2 O 5 After complete dissolution, heating to 140 ℃ for reaction for 3 hours, reacting at 180 ℃ for 24 hours, pouring the polymer solution into deionized water to separate out solid, adding NaHCO 3 The pH of the polymer is regulated to be neutral, the polymer is washed by water for more than 3 times, and the obtained solid is put into an oven for drying. The hydroxy-functionalized OPBI was obtained and designated OH-OPBI-10.
20ml of acetonitrile and 1.15g of TMG are weighed, a 100ml single-neck flask is added, an ice-water bath and 2.38g of 1, 4-dibromobutane are slowly added dropwise under the nitrogen atmosphere, the reaction is carried out for 24 hours at room temperature after the dropwise addition, a crude product is obtained after rotary evaporation, and the crude product is washed with ethyl acetate for 3 times. The crude product was recrystallized from acetonitrile/ethyl acetate. The resulting pentaalkyl guanidine salt was designated [ BrBuTMG ] Br.
Adding OH-OPBI-10 into dimethyl sulfoxide, heating to 80 ℃ to dissolve a polymer to obtain a homogeneous solution, adding [ BrBuTMG ] Br (the molar ratio of the OH-OPBI-10 to the [ BrBuTMG ] Br is 1:2.2), then continuously reacting for 24 hours, pouring the obtained solution into water, washing the precipitated solid with water, and drying to obtain the guanidine salt grafted polymer named TMG/OH-OPBI-10.
TMG/OH-OPBI-10 was added to dimethyl sulfoxide (3 wt% TMG/OH-OPBI-10/DMSO solution), and cast onto glass plates after complete dissolution and oven drying. And then soaking the dried membrane in 85wt% phosphoric acid for 24 hours at 80 ℃, completing phosphoric acid doping, taking out the membrane, and wiping off residual phosphoric acid on the surface to obtain the polybenzimidazole phosphoric acid doped proton exchange membrane.
The structural formula of TMG/OH-OPBI-10 is as follows:
the performance parameters of the prepared exchange membrane test are as follows: the proton conductivity of the membrane reaches 89.45mS cm at 160 DEG C -1 The tensile strength at room temperature after phosphoric acid doping can reach 9.15MPa, and the phosphoric acid has a phosphoric acid adsorption level (ADL) of 16.57 and a swelling rate of 213.65 percent, and the phosphoric acid still remains 82.31 percent after 120 hours of testing at 160 ℃.
Example 2
This example is essentially identical to example 1, except that the OBBA content used in the OH-OPBI-X polycondensation is adjusted to 1.86g and the DHTA amount is adjusted to 0.36g.
The structural formula of TMG/OH-OPBI-20 is as follows:
the performance parameters of the prepared exchange membrane test are as follows: the proton conductivity of the membrane at 160 ℃ is 85.03mS cm -1 The tensile strength of the phosphoric acid doped material at room temperature can reach 9.69MPa, the phosphoric acid doped material has ADL of 16.31 and a swelling rate of 191.86 percent, and the phosphoric acid still has 80.05 percent after 120 hours of testing at 160 ℃.
Example 3
This example is essentially identical to example 1, except that the OBBA content used in the OH-OPBI-X polycondensation is adjusted to 1.63g and the DHTA amount is adjusted to 0.54g.
The structural formula of TMG/OH-OPBI-30 is as follows:
the performance parameters of the prepared exchange membrane test are as follows: the proton conductivity of the membrane reaches 75.35mS cm at 160 DEG C -1 The tensile strength at room temperature after phosphoric acid doping can reach 7.23MPa, and the phosphoric acid has a phosphoric acid adsorption level (ADL) of 13.55 and a swelling rate of 195.40 percent, and the phosphoric acid still remains 77.24 percent after 120 hours of testing at 160 ℃.
Example 4
This example is substantially identical to example 1, except that the molar ratio of OH-OPBI-10 to [ BrBuTMG ] Br is modified to 1:0.5.
the performance parameters of the prepared exchange membrane test are as follows: the proton conductivity of the membrane reaches 66.14mS cm at 160 DEG C -1 The tensile strength at room temperature after phosphoric acid doping can reach 11.88MPa, and the phosphoric acid has a phosphoric acid adsorption level (ADL) of 10.47 and a swelling rate of 165.36 percent, and the phosphoric acid still remains 80.82 percent after 120 hours of testing at 160 ℃.
Example 5
This example is substantially identical to example 4, except that the molar ratio of OH-OPBI-10 to [ BrBuTMG ] Br is modified to 1:1.
the performance parameters of the prepared exchange membrane test are as follows: the proton conductivity of the membrane reaches 78.05mS cm at 160 DEG C -1 The tensile strength at room temperature after phosphoric acid doping can reach 11.13MPa, and the phosphoric acid has a phosphoric acid adsorption level (ADL) of 12.43 and a swelling rate of 183.62 percent, and the phosphoric acid still has 81.29 percent after 120 hours of testing at 160 ℃.
Example 6
It is substantially identical to example 1, except that the guanidine salt is prepared by replacing 1, 4-dibromobutane in the starting material with 1, 3-dibromopropane.
The structural chemical formula is as follows:
the performance parameters of the prepared exchange membrane test are as follows: the film reached 84.25mS cm at 160 DEG C -1 The tensile strength of the polymer can reach 9.54MPa at room temperature after phosphoric acid doping, and the polymer has ADL of 16.01 and a swelling rate of 187.68 percent. The phosphoric acid remained 81.86% after 120h of testing at 160 ℃.
Comparative example 1
This example provides a process for the preparation of a composite proton exchange membrane, which is prepared according to the method of example 1, except that grafting of guanidine groups is not performed.
120g of PPA is weighed into a three-necked flask, nitrogen is introduced, residual air in the PPA is removed by mechanical stirring, and 1.92g of DAB,2.10g of OBBA,0.18g of DHTA and 12g of P are added 2 O 5 After complete dissolution, heating to 140 ℃ for reaction for 3 hours, reacting for 24 hours at 180 ℃, pouring the polymer solution into deionized water to separate out solid, adding NaHCO 3 The pH of the polymer is regulated to be neutral, the polymer is washed by water for more than 3 times, and the obtained solid is put into an oven for drying. The hydroxy-functionalized OPBI was obtained and designated OH-OPBI-10.
The structural general formula is as follows:
OH-OPBI-10 was added to dimethyl sulfoxide (3 wt% OH-OPBI-10/DMSO solution), and cast onto glass plates after complete dissolution and oven drying. And then soaking the dried membrane in 85wt% phosphoric acid for 24 hours at 80 ℃, completing phosphoric acid doping, taking out the membrane, and wiping off residual phosphoric acid on the surface to obtain the polybenzimidazole phosphoric acid doped proton exchange membrane.
The performance parameters of the exchange membrane test are as follows: the film reached 50.51mS cm at 160 ℃ -1 The tensile strength of the polymer at room temperature after phosphoric acid doping can reach 13.67MPa, and the polymer has ADL of 7.53 and a swelling rate of 123.20 percent. Phosphoric acid remained 79.77% after 120h of testing at 160 ℃.
Comparative example 2
This example provides a process for the preparation of a proton exchange membrane which is prepared as in example 1, except that no hydroxyl functionalization and grafting of guanidine groups is performed.
120g of PPA is weighed into a three-necked flask, nitrogen is introduced, residual air in the PPA is removed by mechanical stirring, and 1.92g of DAB,2.31g of OBBA and 12g of P are added 2 O 5 After complete dissolution, heating to 140 ℃ for reaction for 3 hours, reacting at 180 ℃ for 24 hours, pouring the polymer solution into deionized water for cooling, adding NaHCO 3 The pH of the polymer is regulated to be neutral, the polymer is washed by water for more than 3 times, and the obtained solid is put into an oven for drying. Thus obtaining the pure OPBI.
The structural general formula is as follows:
the performance parameters of the exchange membrane test are as follows: the film reached 31.25mS cm at 160 ℃ -1 The tensile strength of the polymer can reach 15.25MPa at room temperature after phosphoric acid doping, and the polymer has ADL of 6.11 and a swelling rate of 90.34 percent. After 120h of testing at 160℃ 75.41% of the phosphoric acid remained.
Comparative example 3
This example provides a process for preparing a composite proton exchange membrane, which is prepared according to the method of example 1, except that the OPBI is not hydroxy-functionalized.
120g of PPA is weighed into a three-necked flask, nitrogen is introduced, residual air in the PPA is removed by mechanical stirring, and 1.92g of DAB,2.31g of OBBA and 12g of P are added 2 O 5 After complete dissolution, heating to 140 ℃ for reaction for 3 hours, reacting at 180 ℃ for 24 hours, pouring the polymer solution into deionized water for cooling, adding NaHCO 3 The pH of the polymer is regulated to be neutral, the polymer is washed by water for more than 3 times, and the obtained solid is put into an oven for drying. Thus obtaining the pure OPBI.
20ml of acetonitrile and 1.15g of TMG are weighed, a 100ml single-neck flask is added, an ice-water bath and 2.38g of 1, 4-dibromobutane are slowly added dropwise under the nitrogen atmosphere, the reaction is carried out for 24 hours at room temperature after the dropwise addition, a crude product is obtained after rotary evaporation, and the crude product is washed with ethyl acetate for 3 times. The crude product was recrystallized from acetonitrile/ethyl acetate. The resulting pentaalkyl guanidine salt was designated [ BrBuTMG ] Br.
And (3) adding OPBI into dimethyl sulfoxide, heating to 80 ℃ to dissolve the polymer, obtaining a homogeneous solution, adding [ BrBuTMG ] Br (the molar ratio of the OPBI to the [ BrBuTMG ] Br is 1:2.2), then continuously reacting for 24 hours, pouring the obtained solution into water, washing the precipitated solid with water, and drying to obtain the guanidine salt grafted polymer named TMG/OPBI.
TMG/OPBI was added to dimethyl sulfoxide (3 wt% TMG/OPBI/DMSO solution), and cast onto glass plates after complete dissolution and oven drying. And then soaking the dried membrane in 85wt% phosphoric acid for 24 hours at 80 ℃, completing phosphoric acid doping, taking out the membrane, and wiping off residual phosphoric acid on the surface to obtain the polybenzimidazole phosphoric acid doped proton exchange membrane.
The structural chemical formula is as follows:
the performance parameters of the prepared exchange membrane test are as follows: the film reached 65.24mS cm at 160 DEG C -1 The tensile strength of the polymer can reach 9.02MPa at room temperature after phosphoric acid doping, and the polymer has ADL of 13.22 and a swelling rate of 190.68 percent. After 120h of testing at 160℃the phosphoric acid remained 77.68%。
The above embodiments are intended to illustrate the design concept of the present invention, and it should be understood that those skilled in the art, after reading the present specification, may make implementation and modification of the present invention, but should not be construed as limiting the scope of the present invention.
Claims (8)
1. The high-temperature proton exchange membrane modified by guanidine salt based on polybenzimidazolyl is characterized by having the following structural formula:
wherein x is an integer value of 1-10, n is the molar ratio of OBBA to DHTA, the value range is 0-1, and 0 and 1 are not taken.
2. A process for the preparation of a polybenzimidazolyl-based guanidinium modified high temperature proton exchange membrane according to claim 1, said process comprising the steps of:
(1) Preparation of hydroxy-functionalized OPBI
Removing residual air in the solvent by mechanical stirring under nitrogen atmosphere, and sequentially adding DAB, OBBA, DHTA and P 2 O 5 After complete dissolution, heating to 140 ℃ for reaction for 3 hours, and polymerizing for 24 hours at 180 ℃; pouring the polymer solution into deionized water to precipitate solid, adding NaHCO 3 Adjusting Ph of the system to be neutral, and drying the solid in an oven to obtain hydroxyl functional OPBI, which is named as OH-OPBI-X; wherein X is the total mole percent of DHTA in OBBA and DHTA;
(2) Preparation of guanidine salts
Dropwise adding haloalkane into acetonitrile solution of tetramethyl guanidine (TMG) in ice water bath and nitrogen atmosphere, transferring to room temperature for reaction for 24 hours after dropwise adding, removing solvent, washing the product with ethyl acetate for 3 times, and removing ethyl acetate to obtain pentaalkyl guanidine salt;
(3) Grafting and film formation
Dissolving the OH-OPBI-X polymer prepared in the step (1) in an organic solvent to form a homogeneous solution, adding a pentaalkyl guanidine salt, continuously stirring for reaction for 24 hours, pouring the solution into water, washing the precipitated solid with water, and then drying to obtain a product named TMG/OH-OPBI-X;
dissolving TMG/OH-OPBI-X in an organic solvent to form a homogeneous solution, casting the film solution onto a glass plate, and drying in an oven to obtain the film.
3. The method for preparing a polybenzimidazolyl-based guanidine salt modified high-temperature proton exchange membrane according to claim 2, wherein the solvent in the step (1) is PPA or eaton reagent.
4. The method for preparing a high temperature proton exchange membrane modified with a guanidinium based on polybenzimidazolyl as set forth in claim 2, wherein in the step (1), the molar ratio of DAB to (OBBA+DHTA) is 1:1, the percentage values of OBBA and DHTA are 0 to 1, and are not 0 and 1, OBBA+DHTA is 1, P 2 O 5 The dosage of (2) is 3-4 times of the sum of DAB, OBBA, DHTA.
5. The method for preparing the polybenzimidazolyl-based guanidine salt modified high-temperature proton exchange membrane according to claim 2, wherein the molar ratio of Tetramethylguanidine (TMG) to haloalkane in the step (2) is 1:1.1, halogen in haloalkane comprises fluorine, chlorine, bromine and iodine, and the number of alkyl groups is 1-10.
6. The method for preparing the polybenzimidazolyl-based guanidine salt modified high-temperature proton exchange membrane according to claim 2, wherein the organic solvent in the step (3) is: dimethyl sulfoxide, N-dimethylformamide or N-methylpyrrolidone; the temperature at which the OH-OPBI-X polymer was dissolved in the organic solvent was 80 ℃.
7. The method for preparing the polybenzimidazolyl-based guanidine salt modified high-temperature proton exchange membrane according to claim 2, wherein the molar ratio of the OH-OPBI-X polymer to the pentaalkyl guanidine salt in the step (3) is 1:a, and the value of a is 0.1-2.2.
8. Use of a high temperature proton exchange membrane based on a modification of a guanidinium salt of polybenzimidazolyl group according to claim 1 for a fuel cell.
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