CN104485467B - PBI-based polysiloxane and phosphonic acid high-temperature proton exchange film and preparation method thereof - Google Patents
PBI-based polysiloxane and phosphonic acid high-temperature proton exchange film and preparation method thereof Download PDFInfo
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- CN104485467B CN104485467B CN201410782297.1A CN201410782297A CN104485467B CN 104485467 B CN104485467 B CN 104485467B CN 201410782297 A CN201410782297 A CN 201410782297A CN 104485467 B CN104485467 B CN 104485467B
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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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
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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
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention belongs to the technical field of fuel batteries, and relates to a PBI-based polysiloxane and phosphonic acid high-temperature proton exchange film and a preparation method thereof. The PBI-based polysiloxane and phosphonic acid high-temperature proton exchange film disclosed by the invention is prepared through the following method: dispersing polysiloxane and phosphonic acid in dimethylacetamide, and preparing to obtain a polysiloxane and phosphonic acid gel; then dissolving PBI in dimethylacetamide to obtain PBI polymer solution; then uniformly mixing the polysiloxane and phosphonic acid gel with the PBI polymer solution, then preparing by a tape-casting film-forming technique to obtain the PBI-based polysiloxane and phosphonic acid high-temperature proton exchange film. The doping amount of phosphonic acid is low and phosphonic acid is not liable to exude when the high-temperature proton exchange film prepared by the preparation method disclosed by the invention achieves a certain proton conductivity, and the high-temperature proton exchange film has a high proton conductivity under a high-temperature and low-humidity condition; moreover, the medium-temperature proton exchange film is good in flexibility, high in mechanical strength, and good in durability in a high-temperature fuel battery.
Description
Technical field
The invention belongs to field of fuel cell technology, is related to a kind of polysiloxanes phosphonic acids high temperature proton exchange based on PBI
Film and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) has transformation efficiency height, energy density is big, capable of fast starting and environment is friendly
The advantages of good.It cannot be only used for building distributed power station, also particularly suitable as movable power source, be military and civilian it is general one
Novel moveable electrical source of power is planted, also with the optimal candidate power supply that chlor-alkali plant byproduct hydrogen gas generate electricity.Therefore, PEMFC is obtained
Arrive rapid development, it is considered to be one of most promising clean energy resource switch technology, and cause the research of numerous scholars
Interest.PEM (PEM) is the vitals in Proton Exchange Membrane Fuel Cells, and its performance to PEM has
Vital impact, its Main Function is proton conducting, while preventing the oxygen of negative electrode and the hydrogen Cross slot interference of anode.
At present most widely used PEM is water in perfluoro sulfonic acid membrane, but the proton conductivity heavy dependence film of perfluoro sulfonic acid membrane
Content.In order to improve the toleration of Pt electrode pairs CO, when can improve the operation temperature of fuel cell, but temperature higher than 100 DEG C
Moisture evaporation can cause the proton conductivity degradation of perfluoro sulfonic acid membrane in film.So the Water Heat Pipes in order to simplify fuel cell
Reason system, the toleration for improving Pt electrode pairs CO, it is necessary to prepare a kind of incomplete high temperature proton exchange film for relying on water conduction.
Silicone matrix has the advantages that good thermostability, hydrophobicity, but simple polysiloxane film is crisp and hard,
The base material of PEM is cannot function as, its submissive and processing characteristics can be improved by adding organic component.Phosphonic acids is
The middle strong acid that a kind of hygroscopicity is strong, boiling point is high, it has both sexes, can not only ionize out proton but also can receive proton (P-O-H can
To ionize out proton, P=O can receive proton), phosphonic acids forms continuous hydrogen bond and realizes proton by the fracture of hydrogen bond and formation
Transmission, so, phosphonic acids can serve as the proton conduction unit of high temperature proton exchange film.At present, the PEM based on phosphonic acids
There are three shortcomings：Phosphonic acids oozes out during use, film is hard and crisp, proton conductivity is not high.
The content of the invention
It is an object of the invention to provide a kind of polysiloxanes phosphonic acids high temperature proton exchange film and its preparation side based on PBI
Method.The PEM that the present invention is prepared has more high-quality electron conductivity and excellent in mechanical performance under high temperature, low humidity.
To solve technical problem proposed by the present invention, the technical solution adopted in the present invention is：
A kind of polysiloxanes phosphonic acids high temperature proton exchange film based on PBI, is prepared via a method which to obtain：First will be poly-
Siloxanes, phosphonic acids are dispersed in dimethyl acetylamide, and using sol-gel technology polysiloxanes phosphonic acids gel is prepared；Again
PBI is dissolved in dimethyl acetylamide and obtains PBI polymer solutions；Then by polysiloxanes phosphonic acids gel and PBI polymer
After solution mix homogeneously, prepared based on the polysiloxanes phosphonic acids high temperature proton exchange film of PBI using the tape casting film-forming process.
A kind of preparation method of the polysiloxanes phosphonic acids high temperature proton exchange film based on PBI, comprises the steps：
(1) drying of raw material：Polysiloxanes, phosphonic acids, PBI are placed in vacuum drying oven and are fully dried；
(2) preparation of polysiloxanes phosphonic acids gel：By polysiloxanes：The mol ratio of phosphonic acids is 1:0.5 weighs raw material, takes one
Quantitative dimethyl acetylamide (DMAc), polysiloxanes are slowly dropped in dimethyl acetylamide, are stirred half an hour, then are slowly added
Enter phosphonic acids, be stirred at room temperature 12~24 hours, obtain stablizing limpid polysiloxanes phosphonic acids gel；
(3) preparation of PBI (poly- 2,2 '-phenyl -5,5 '-bisbenzimidazole) polymer solution：PBI is dissolved in into one
Quantitative dimethyl acetylamide, stirs 6~8 hours, obtains the PBI polymer solutions of brown color；
(4) based on PBI polysiloxanes phosphonic acids high temperature proton exchange film preparation：By the polysiloxanes phosphine in step (2)
Acid gel is slowly added in the PBI polymer solutions that step (3) is obtained, and is stirred 12~24 hours, it is to be mixed it is uniform after will mixing
Liquid is poured in politef mould, is prepared based on the polysiloxanes phosphonic acids high temperature matter of PBI using the tape casting film-forming process
Proton exchange.
By such scheme, the polysiloxanes are 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane.
By such scheme, the phosphonic acids is ATMP.
By such scheme, the mass content of PBI is in the polysiloxanes phosphonic acids high temperature proton exchange film based on PBI
5wt%~50wt%.
By such scheme, the tape casting film-forming process is：Mixed liquor is poured in politef mould, it is dry in vacuum
It is dried 48 hours at 80 DEG C in dry case, is warming up to 120 DEG C of dryings 2 hours, obtains based on the polysiloxanes phosphonic acids high temperature proton of PBI
Exchange membrane.
In the present invention, the polysiloxanes, phosphonic acids and dimethyl acetylamide are analyzes pure, and purity is more than 98wt%.
The present invention adopts phosphonic acids as proton conduction unit, in sol-gel with organopolysiloxane network formationization
Learn key, it is possible to reduce phosphonic acids oozing out in battery operation, strengthen matter of the high temperature proton exchange film under high temperature and low humidity
Sub- conductivity；Further, the present invention makees presoma using 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane (EHTMS),
The PEM that synthesis can be made has longer organic chain, so as to greatly improve the pliability of the PEM；Using
Poly- PBI can improve the mechanical performance of film as polymeric substrates, and the imidazole ring in PBI can also form continuous hydrogen with phosphonic acids
Key, the doping of phosphonic acids when reduction reaches certain proton conductivity.
The present invention compared with prior art, has the following advantages that：
1) prepared based on the polysiloxanes phosphonic acids high temperature proton exchange film of PBI using the inventive method, it is secondary with high income
Reaction is few, reaction temperature low (room temperature), the simple advantage of method, and instrument is simple, simple to operate；
2) the polysiloxanes phosphonic acids high temperature proton exchange film based on PBI prepared by this method, in high temperature, low humidity, a small amount of phosphine
There is higher proton conductivity under the conditions of acid doping, and phosphonic acids difficulty is oozed out；
3) this method prepare the polysiloxanes phosphonic acids high temperature proton exchange film pliability based on PBI is good, high mechanical strength,
Good endurance in high-temperature fuel cell；
4) fuel cell that the polysiloxanes phosphonic acids high temperature proton exchange film based on PBI prepared using this method is assembled,
Operating temperature is high, can substantially reduce CO and catalyst is poisoned, and improves the activity of catalyst, improves the output work of fuel cell
Rate, simplifies the hydro-thermal management of battery.
Specific embodiment
For a better understanding of the present invention, present disclosure is further elucidated with reference to embodiment, but the present invention
Content is not limited solely to the following examples.
Raw material used is and analyzes pure in following embodiments, and purity is more than 98wt%.
Embodiment 1：
A kind of polysiloxanes phosphonic acids high temperature proton exchange film based on PBI, the method for being prepared via a method which is obtained：
1) preparation of polysiloxanes phosphonic acids gel：According to each raw material 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane
(EHTMS)：The mol ratio of ATMP (ATMP) is 1：0.5(EHTMS:2.4631g,ATMP:1.4193g),
DMAc 20ml weigh raw material, and in DMAc EHTMS is slowly added to, and stir in Deca, and ATMP is slowly added to after stirring,
Stir 24 hours under room temperature, obtain the gel of stable clarification.
2) preparation of PBI polymer solutions：Weigh 0.2084g PBI to be dissolved in 15ml DMAc, obtain brown color
PBI polymer solutions.
3) by PBI polymer solutions：The mass ratio 5 of polysiloxanes phosphonic acids gel：95 weigh, and the two is stirred into equal to mixing
It is even, pour mixed liquor into politef mould and be put into vacuum drying oven, processing at 80 DEG C makes solvent volatilize in 48 hours, subsequently rises
Temperature to 120 DEG C are vacuum dried 2 hours, obtain based on the polysiloxanes phosphonic acids high temperature proton exchange film of PBI.
PBI contents are the film of 5wt%, and swellbility 5% is not decomposed at 200 DEG C of high temperature, and the application met under hot conditionss will
Ask, proton conductivity 0.082S/cm, tensile strength 40.34Mpa, the mass loss 30.31% after 48h in Fenton reagent, soak
Fragmentate without division after bubble two weeks.
Embodiment 2：
A kind of polysiloxanes phosphonic acids high temperature proton exchange film based on PBI, the method for being prepared via a method which is obtained：
1) preparation of polysiloxanes phosphonic acids gel：According to each raw material EHTMS：The mol ratio of ATMP is：1：0.5(EHTMS:
1.23105g,ATMP:0.7096g), DMAc 20ml weigh raw material, and in DMAc EHTMS is slowly added to, and stir in Deca,
ATMP is slowly added to after stirring, is stirred 24 hours under room temperature, obtain the gel of stable clarification.
2) preparation of PBI polymer solutions：Weigh 0.2199g PBI to be dissolved in 15ml DMAc, obtain brown color
PBI polymer solutions.
3) by PBI polymer solutions：Polysiloxanes phosphonic acids gel mass ratio 10：90 weigh, and the two is stirred into equal to mixing
It is even, pour mixed liquor into politef mould and be put into vacuum drying oven, processing at 80 DEG C makes solvent volatilize in 48 hours, subsequently rises
Temperature to 120 DEG C are vacuum dried 2 hours, obtain based on the polysiloxanes phosphonic acids high temperature proton exchange film of PBI.
PBI contents are 10% film, and swellbility 5% is not decomposed at 200 DEG C of high temperature, and the application met under hot conditionss will
Ask, proton conductivity 0.075S/cm, tensile strength 43.27Mpa, the mass loss 28.43% after 48h in Fenton reagent, soak
Fragmentate without division after bubble two weeks.
Embodiment 3：
A kind of polysiloxanes phosphonic acids high temperature proton exchange film based on PBI, the method for being prepared via a method which is obtained：
1) preparation of polysiloxanes phosphonic acids gel：According to each raw material EHTMS：The mol ratio of ATMP is：1：0.5(EHTMS:
0.6155g,ATMP:0.3548g), DMAc 20ml weigh raw material, and in DMAc EHTMS is slowly added to, and stir in Deca, stir
ATMP is slowly added to after mixing uniformly, is stirred 24 hours under room temperature, obtain the gel of stable clarification.
2) preparation of PBI polymer solutions：Weigh 0.3234g PBI to be dissolved in 15ml DMAc, obtain brown color
PBI polymer solutions；
3) by PBI polymer solutions：The mass ratio 25 of polysiloxanes phosphonic acids gel：75 weigh, and the two is stirred to mixing
Uniformly, pour mixed liquor into politef mould and be put into vacuum drying oven, processing at 80 DEG C makes solvent volatilize in 48 hours, subsequently
It is warming up to 120 DEG C to be vacuum dried 2 hours, obtains based on the polysiloxanes phosphonic acids high temperature proton exchange film of PBI.
PBI contents are 25% film, and swellbility 5% is not decomposed at 200 DEG C of high temperature, and the application met under hot conditionss will
Ask, proton conductivity 0.077S/cm, tensile strength 45.43Mpa, the mass loss 26.28% after 48h in Fenton reagent, soak
Fragmentate without division after bubble two weeks.
Embodiment 4：
A kind of polysiloxanes phosphonic acids high temperature proton exchange film based on PBI, the method for being prepared via a method which is obtained：
1) preparation of polysiloxanes phosphonic acids gel：According to each raw material EHTMS：The mol ratio of ATMP is：1：0.5(EHTMS:
0.2463g,ATMP:0.14963g), DMAc 20ml weigh raw material, and in DMAc EHTMS is slowly added to, and stir in Deca,
ATMP is slowly added to after stirring, is stirred 24 hours under room temperature, obtain the gel of stable clarification.
2) preparation of PBI polymer solutions：Weigh 0.3959g PBI to be dissolved in 15ml DMAc, obtain brown color
PBI polymer solutions.
3) by PBI polymer solutions：The mass ratio 50 of polysiloxanes phosphonic acids gel：50 weigh, and the two is stirred to mixing
Uniformly, pour mixed liquor into politef mould and be put into vacuum drying oven, processing at 80 DEG C makes solvent volatilize in 48 hours, subsequently
It is warming up to 120 DEG C to be vacuum dried 2 hours, obtains based on the polysiloxanes phosphonic acids high temperature proton exchange film of PBI.
PBI contents are 50% film, and swellbility 5% is not decomposed at 200 DEG C of high temperature, and the application met under hot conditionss will
Ask, proton conductivity 0.070S/cm, tensile strength 55.68Mpa, the mass loss 23.97% after 48h in Fenton reagent, soak
Fragmentate without division after bubble two weeks.
Each raw material cited by the present invention, and bound, the interval value of each raw material of the invention, and technological parameter
The bound of (such as temperature, time), interval value can realize the present invention, embodiment numerous to list herein.
Claims (2)
1. a kind of preparation method of the polysiloxanes phosphonic acids high temperature proton exchange film based on PBI, it is characterised in that including following step
Suddenly：
（1）The drying of raw material：Polysiloxanes, phosphonic acids, PBI are placed in vacuum drying oven and are fully dried；
（2）The preparation of polysiloxanes phosphonic acids gel：By polysiloxanes：The mol ratio of phosphonic acids is 1:0.5 weighs raw material, takes a certain amount of
Dimethyl acetylamide, polysiloxanes are slowly dropped in dimethyl acetylamide, stir half an hour, are slow added into phosphonic acids, room
Temperature stirring 12~24 hours, must stablize limpid polysiloxanes phosphonic acids gel；
（3）The preparation of PBI polymer solutions：PBI is dissolved in a certain amount of dimethyl acetylamide, is stirred 6~8 hours, obtained
The PBI polymer solutions of brown color；
（4）Preparation based on the polysiloxanes phosphonic acids high temperature proton exchange film of PBI：By step（2）In polysiloxanes phosphonic acids coagulate
Glue is slowly added into step（3）In the PBI polymer solutions for obtaining, stir 12~24 hours, it is to be mixed it is uniform after by mixed liquor
In pouring politef mould into, prepared based on the polysiloxanes phosphonic acids high temperature proton of PBI using the tape casting film-forming process
Exchange membrane；
The polysiloxanes are 2-（3,4- epoxycyclohexyls）Ethyl trimethoxy silane；The phosphonic acids is aminotrimethylene phosphine
Acid；The mass content of PBI is 5wt% ~ 50wt% in the polysiloxanes phosphonic acids high temperature proton exchange film based on PBI.
2. preparation method according to claim 1, it is characterised in that the tape casting film-forming process is：Mixed liquor is fallen
In entering politef mould, it is dried 48 hours at 80 DEG C in vacuum drying oven, is warming up to 120 DEG C of dryings 2 hours, obtains base
In the polysiloxanes phosphonic acids high temperature proton exchange film of PBI.
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| CN105098215B (en) * | 2015-08-19 | 2017-05-31 | 武汉理工大学 | A kind of phosphonic acids radical siloxane PEM of hydrolysis-stable and preparation method thereof |
| CN105895943B (en) * | 2016-05-03 | 2018-09-14 | 武汉理工大学 | A kind of phosphonic-acid grafted polybenzimidazoles high temperature proton exchange film and preparation method thereof |
| CN106684414B (en) * | 2016-11-23 | 2019-05-10 | 长春工业大学 | Fuel cell organic-inorganic compoiste high temperature proton exchange film and preparation method thereof |
| CN106558717B (en) * | 2016-11-23 | 2019-05-10 | 长春工业大学 | Fuel cell high temperature compoiste proton exchange film and preparation method thereof |
| CN106549171B (en) * | 2016-12-07 | 2019-03-22 | 黄河科技学院 | A kind of cross-linking type polybenzimidazoles high temperature proton exchange film and preparation method thereof with the high conductivity of high antioxygenic property |
| CN107104242B (en) * | 2017-05-03 | 2020-01-14 | 武汉理工大学 | Polysiloxane polyphosphonic acid doped SPEEK high and low temperature universal proton exchange membrane and preparation method thereof |
| CN111029632B (en) * | 2019-12-23 | 2021-02-19 | 珠海冠宇电池股份有限公司 | Phosphonated polyolefin/benzimidazole polymer composite proton exchange membrane and preparation method and application thereof |
| CN112142981B (en) * | 2020-09-18 | 2022-03-01 | 珠海冠宇电池股份有限公司 | Phosphonic hyperbranched polybenzimidazole-polysiloxane block copolymer and preparation method and application thereof |
| CN112126063B (en) * | 2020-09-18 | 2022-04-19 | 珠海冠宇电池股份有限公司 | Polybenzimidazole-polysiloxane block copolymer and preparation method and application thereof |
| CN112142980B (en) * | 2020-09-18 | 2022-03-01 | 珠海冠宇电池股份有限公司 | Hyperbranched polybenzimidazole-polysiloxane block copolymer and preparation method and application thereof |
| CN112980201B (en) * | 2021-02-05 | 2022-08-30 | 珠海冠宇电池股份有限公司 | Phosphonic acid modified graphene oxide cross-linked polybenzimidazole-polysiloxane block copolymer composite material |
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| US7897650B2 (en) * | 2007-08-31 | 2011-03-01 | Sayre Jay R | Ionically conductive polymers for use in fuel cells |
| US20120219879A1 (en) * | 2009-09-24 | 2012-08-30 | Ewe-Forschungszentrum Für Energietechnologie E.V. | Proton exchange membrane comprising polymer blends for use in high temperature proton exchange membrane fuel cells |
| CN101792470B (en) * | 2010-03-18 | 2012-03-07 | 武汉理工大学 | Preparation method of phosphonic acid group alkoxysilane for intermediate-temperature proton exchange membrane |
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