CN106549171B - A kind of cross-linking type polybenzimidazoles high temperature proton exchange film and preparation method thereof with the high conductivity of high antioxygenic property - Google Patents
A kind of cross-linking type polybenzimidazoles high temperature proton exchange film and preparation method thereof with the high conductivity of high antioxygenic property Download PDFInfo
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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
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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 discloses a kind of cross-linking type polybenzimidazoles high temperature proton exchange film and preparation method thereof with the high conductivity of high antioxygenic property, the cross linking membrane is using polybenzimidazoles as polymer backbone, pass through polymerization reaction, it is crosslinking agent using vinyl phosphonic acid and vinyl triazole, the reticular structure of crosslinking is formed in film, and the free radical quencher for improving film antioxygenic property is doped in film, prepare the high temperature proton exchange film with high antioxygenic property and high conductivity.Cross-linking type high temperature proton exchange film proposed by the present invention has preferable Proton conducting ability and excellent dimensional stability under not humidification conditions, and there is high antioxygenic property, thoroughly solve polybenzimidazoles/phosphoric acid film phosphoric acid losing issue, and polymer film by the bottleneck that free radical is attacked and is degraded can be applied in high temperature proton exchange film fuel cell, direct alcohol fuel cell, electrochemical sensor or other electrochemical appliances that proton exchange membrane is used as to use.
Description
Technical field
The invention belongs to fuel cell material technical fields, and in particular to a kind of with the high conductivity of high antioxygenic property
Cross-linking type polybenzimidazoles high temperature proton exchange film and preparation method thereof.
Background technique
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of efficient, cleaning, environmental-friendly power generator, is electronic vapour
The ideal power source of vehicle can also be used as the Military Powers or portable power etc. such as dispersion power station, submarine and spacecraft, have very
Wide application prospect.However now widely used is perfluor type sulfonic acid membrane cell using Nafion as representative, but
The proton conducting ability of this kind of proton exchange membrane is influenced very big by water content in film and temperature, and alcohol-rejecting ability is poor, the work of PEMFC
Make temperature no more than 80 DEG C.Since PEMFC is limited by operating temperature, so that it faces CO tolerance in practical application
The problems such as difference, the hydro-thermal difficult management of system.Therefore PEMFC running temperature is increased to 100 DEG C or more, it can effectively gram
The above problem of tradition Nafion base PEMFC is taken, the fuel cell (FC) of this type is normally referred to as high temperature proton exchange film
Fuel cell (HT-PEMFC) is an important developing direction of PEMFC technology.
HT-PEMFC system has the following advantages: 1) electrochemical reaction speed improves, and effectively reduces electrochemical cathode polarization
Overpotential allows to reduce catalyst load amount, allow using non-platinum catalyst；2) humidification requirements of reaction gas are reduced；3) electric
Pool inner water exists with gas phase simplifies hydro-thermal management；In addition, HT-PEMFC simplifies FC cooling system to a certain extent.In view of
HT-PEMFC tempting development prospect has carried out the development of HT-PEMFC critical material extensively both at home and abroad, including high temperature proton is handed over
Change film, catalyst and carrier etc., and achieve preferable PRELIMINARY RESULTS, wherein high temperature proton exchange film be research hot spot it
One.
The research of HT-PEMFC proton exchange membrane is concentrated mainly on polybenzimidazoles (PBI) at present, it is in 1959
Year is reported for the first time in United States Patent (USP), and Hoechst Celanese company, the U.S. introduces PBI film product to the market within 1988.Such as
The present, PBI is as polymer-based material the most outstanding in engineering thermoplasties, in the high temperature proton exchange for being used as HT-PEMFC
Huge validity and feasibility are shown in terms of film.But PBI type membrane material (T >=150 DEG C) in hot operation, meeting can not
It degrades with avoiding.
The study found that oxygen penetrates into anode-side by film, in anode Pt and micro transition in fuel cell operation
Under the catalytic action of metal ion, the free radicals such as OH and HOO are formed, the nitrogen-containing group on OH free radical attack PBI main chain,
HOO free radical attacks the C-H bond on phenyl ring, makes PBI backbone breaking；High-temperature oxidation environment is also easy to make on PBI main chain simultaneously
Two Amino End Groups oxidation, carboxyl end group occur decarboxylic reaction generate phenylene free radical.These free radicals generated can aggravate PBI
The degradation of film, causes battery performance to decline to a great extent.Room Jian Hua etc. is (more using epoxides (CN 200710171866.9), dihalo-
Halogen) alkane (CN 200710171865.4) and maleic anhydride (CN 200710171867.3) be to an end ammonia on PBI main chain
Base carries out crosslinking protection, to slow down the degradation of film；Li Zhongfang et al. uses urea (101768270 A of CN), as Amino End Group
Protectiveness reagent PBI is modified.Variable valency metal type free base quencher (such as CeO2、MnO2Deng) or change polymerization
The free radical generated in HT-PEMFC operational process can be effectively quenched in object structure, to slow down the degradation of PBI film.
It is easy the problems such as to be attacked and degraded by free radical in conclusion obtaining such proton exchange membrane polymeric substrates at present
Its commercialized application is restricted, by adding free radical quencher in film, constructing cross-linked structure in film, can effectively be kept away
Exempt from free radical attack and degrade, promotes the service life of film, and improve the dimensional stability of film.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of with the high conductivity of high antioxygenic property
Cross-linking type polybenzimidazoles high temperature proton exchange film and preparation method thereof, by passing through using polybenzimidazoles as polymer backbone
Polymerization reaction is crosslinking agent using vinyl phosphonic acid and vinyl triazole, forms the reticular structure of crosslinking in film, and in film
In be doped with improve film antioxygenic property free radical quencher, prepare have high antioxygenic property and high conductivity high temperature
Proton exchange membrane.Cross-linking type high temperature proton exchange film proposed by the present invention has preferable Proton conducting under not humidification conditions
Ability and excellent dimensional stability, and there is high antioxygenic property, it thoroughly solves polybenzimidazoles/phosphoric acid film phosphoric acid and is lost
The bottleneck that problem and polymer backbone are degraded by free radical attack.
To achieve the goals above, the technical solution adopted by the present invention are as follows:
A kind of preparation side of the cross-linking type polybenzimidazoles high temperature proton exchange film with the high conductivity of high antioxygenic property
Method, comprising the following steps:
(1) by 0.5 ~ 2 g1- vinyl -1,2,4- triazole is dissolved in 10 ~ 20 mL high boiling solvents, is added chain and is drawn
Agent azodiisobutyronitrile is sent out, wherein the mass content of chain initiator is the 20 ~ 50% of high boiling solvent, is put into oil bath, reaction 24
~ 48 h, reaction temperature are 50 ~ 80 DEG C；
(2) 0.2 ~ 1 g polybenzimidazoles will be added in solution, after stirring and dissolving, add vinyl phosphonic acid, stirring and dissolving
Afterwards, azodiisobutyronitrile is added, 1 ~ 2 h, nitrogen protection is stirred at room temperature, gas flow is 100 mL/min；
(3) solution is put into oil bath, is stirred at 50 ~ 100 DEG C, react 12 ~ 48 h；
(4) 5 ~ 10 mL high boiling solvents will be continuously added in solution, and after stirring 30 min, free radical quencher is added, surpasses
Sound stirs 30 min, pours into casting film plate, is evaporated solvent at 60 ~ 80 DEG C, obtained high temperature proton exchange film is carefully taken off
Under, it impregnates in ethanol, it is dry after washing；
(5) the cross-linking type high temperature proton exchange film after drying is immersed in phosphoric acid solution, at 60 ~ 120 DEG C impregnate 24 ~
It is taken out after 48 h, obtains high temperature proton exchange film.
Preferably, the additional amount of vinyl phosphonic acid described in step (2) is 1- vinyl -1,2,4- triazole mole matter
The 100% ~ 300% of amount；The additional amount of azodiisobutyronitrile is the 1 ~ 5% of 1- vinyl -1,2,4- triazole molal weight；
Preferably, step (1), high boiling solvent described in (4) are n,N-dimethylacetamide or N-Methyl pyrrolidone.
Preferably, the free radical quencher is one kind of ceria, silica, manganese dioxide, additional amount
It is the 0.1% ~ 0.9% of polybenzimidazoles quality；
Preferably, the mass fraction of phosphoric acid is 50% ~ 85% in phosphoric acid solution described in step (5).
The cross-linking type polybenzimidazoles high temperature with the high conductivity of high antioxygenic property obtained using above-mentioned preparation method
Proton exchange membrane.
Cross-linking type polybenzimidazoles high temperature proton exchange film provided by the invention with the high conductivity of high antioxygenic property
And preparation method thereof, it has the advantages that compared with prior art
1. it is polymer backbone that polybenzimidazoles, which is respectively adopted, in the present invention, by polymerization reaction, using vinyl phosphonic acid with
Vinyl triazole is crosslinking agent, and the reticular structure of crosslinking is formed in film, and is doped in film and improves film inoxidizability
Can free radical quencher, the structure of composite membrane as made from self-crosslinking is uniform, be suitable for anhydrous system, operating temperature 120 ~
200 DEG C of high temperature proton exchange film fuel cell.
2. cross-linking type high temperature proton exchange film proposed by the present invention has preferable Proton conducting under not humidification conditions
Ability and excellent dimensional stability, and there is high antioxygenic property, it thoroughly solves polybenzimidazoles/phosphoric acid film phosphoric acid and is lost
The bottleneck that problem and polymer estimation are degraded by free radical attack.
3. polyvinylphosphonic acid and triazole in crosslinking agent of the present invention, can effectively adsorb phosphoric acid molecules,
Improve the long-time stability of film conductivity in cell operation.
4. the cross-linking type polybenzimidazoles high temperature proton exchange proposed by the present invention with the high conductivity of high antioxygenic property
Film can be applied to high temperature proton exchange film fuel cell, direct alcohol fuel cell, electrochemical sensor or other electrochemistry
It is used in device as proton exchange membrane.
Detailed description of the invention
Fig. 1 is the cross-linking type polybenzimidazoles high temperature proton obtained with the high conductivity of high antioxygenic property of embodiment 1
The conductivity variation with temperature figure of exchange membrane and tradition PBI composite membrane；
Fig. 2 is the cross-linking type polybenzimidazoles high temperature proton obtained with the high conductivity of high antioxygenic property of embodiment 2
The cell polarization curves figure of exchange membrane and tradition PBI composite membrane.
Specific embodiment
Polybenzimidazoles (PBI, CAS:25928-81-8) used is purchased from FuMA-Tech company in following example；N,N-
Dimethyl acetamide (DMAC, CAS:127-19-5), N-Methyl pyrrolidone (NMP, CAS:872-50-4) are purchased from Tianjin
Great Mao chemical reagents corporation；1- vinyl -1,2,4- triazole (CAS:2764-83-2) is limited purchased from Shanghai source leaf biotechnology
Company；Azodiisobutyronitrile (AIBN, CAS:78-67-1) is purchased from Tianjin great Mao chemical reagents corporation；Vinyl phosphonic acid
(CAS:1746-03-8) it is purchased from Chengdu Hua Xia chemical reagent Co., Ltd；Ceria, manganese dioxide, silica, phosphoric acid
Purchased from Shanghai Aladdin biochemical technology limited liability company.
Embodiment 1
A kind of preparation side of the cross-linking type polybenzimidazoles high temperature proton exchange film with the high conductivity of high antioxygenic property
Method, comprising the following steps:
(1) by 2 g1- vinyl -1,2,4- triazole is dissolved in 20 mL N-Methyl pyrrolidones, adds chain initiation
Agent azodiisobutyronitrile, wherein the mass content of chain initiator is the 25% of high boiling solvent；It is put into oil bath, reacts 48 h, instead
Answering temperature is 50 DEG C；
(2) it will be added 1 g polybenzimidazoles in solution, after stirring and dissolving, add vinyl phosphonic acid, after stirring and dissolving,
Azodiisobutyronitrile is added, 2 h, nitrogen protection are stirred at room temperature, gas flow is 100 mL/min；
(3) solution is put into oil bath, is stirred at 100 DEG C, react 48 h；
(4) it will continue to add 10 mL N-Methyl pyrrolidones in solution, after stirring 30 min, free radical quencher two be added
Manganese oxide is stirred by ultrasonic 30 min, pours into casting film plate, be evaporated solvent at 80 DEG C, and obtained high temperature proton exchange film is small
The heart is taken off, impregnates in ethanol, dry after washing；
(5) the cross-linking type high temperature proton exchange film after drying is immersed in phosphoric acid solution, after 48 h are impregnated at 120 DEG C
It takes out, obtains high temperature proton exchange film.
In order to be handed over the cross-linking type polybenzimidazoles high temperature proton obtained above with the high conductivity of high antioxygenic property
It changes film to compare, the PBI film with a thickness of 50 μm, then impregnation of phosphoric acid is prepared using solution casting method, PBI/ phosphoric acid film is made,
Specific preparation step are as follows: the N-Methyl pyrrolidone solution of PBI is poured in glass mold, 25 h are dried in vacuo at 80 DEG C,
Obtain PBI film；PBI film is immersed in 60 h in 60 DEG C of phosphoric acid, takes out and in 80 DEG C of dry 24 h, is denoted as traditional PBI and answers
Close film；Wherein, the mass fraction of PBI is 2% in the N-Methyl pyrrolidone solution of PBI, and the concentration of phosphoric acid is 70 wt%.
The cross-linking type polybenzimidazoles high temperature proton exchange film obtained with the high conductivity of high antioxygenic property of embodiment 1
And tradition PBI composite membrane, testing conductivity variation with temperature figure.To there is the high electricity of high antioxygenic property made from embodiment 1
The cross-linking type polybenzimidazoles high temperature proton exchange film and tradition PBI composite membrane of conductance are cut into having a size of the mm's of 40 mm × 10
Rectangular sheet, the cross-linking type polybenzimidazoles high temperature proton that then will there is the high conductivity of high antioxygenic property made from embodiment 1
Exchange membrane and tradition PBI composite membrane are respectively placed in conductivity fixture, and fixture is put in a vacuum drying oven, is protected at 90 DEG C
3 h are held, then temperature rises to 170 DEG C from 90 DEG C, the conductivity of lower film is tested every 10 DEG C, as a result as shown in Figure 1.
It will be seen from figure 1 that the cross-linking type polybenzimidazoles obtained with the high conductivity of high antioxygenic property of embodiment 1
Compared with traditional PBI composite membrane, conductivity is substantially improved high temperature proton exchange film, this is because triazole is deposited in cross-linked structure
More phosphate adsorption sites are being provided, to improve the conductivity of film.
Embodiment 2
A kind of preparation side of the cross-linking type polybenzimidazoles high temperature proton exchange film with the high conductivity of high antioxygenic property
Method, comprising the following steps:
(1) by 1.5 g1- vinyl -1,2,4- triazole is dissolved in 15 mL N-Methyl pyrrolidone solvents, is added
Chain initiator azodiisobutyronitrile, wherein the mass content of chain initiator is the 38% of high boiling solvent, is put into oil bath, is reacted
28 h, reaction temperature are 80 DEG C；
(2) it will be added 0.8 g polybenzimidazoles in solution, after stirring and dissolving, add vinyl phosphonic acid, stirring and dissolving
Afterwards, azodiisobutyronitrile is added, 2 h, nitrogen protection are stirred at room temperature, gas flow is 100 mL/min；
(3) solution is put into oil bath, is stirred at 50 DEG C, react 48 h；
(4) 8 mL N-Methyl pyrrolidone solvents will be continuously added in solution, after stirring 30 min, free radical are added and quenches
Go out agent ceria, and 30 min are stirred by ultrasonic, pours into casting film plate, is evaporated solvent at 70 DEG C, and obtained high temperature proton is handed over
It changes film carefully to take off, impregnate in ethanol, it is dry after washing；
(5) the cross-linking type high temperature proton exchange film after drying is immersed in phosphoric acid solution, 24 h is impregnated at 80 DEG C, after
It takes out, obtains high temperature proton exchange film.
In order to be compared with cross-linking type polybenzimidazoles obtained above/polyethylene triazole high temperature proton exchange film,
PBI film with a thickness of 50 μm, then impregnation of phosphoric acid are prepared using solution casting method, PBI/ phosphoric acid film, specific preparation step is made
Are as follows: the N-Methyl pyrrolidone solution of PBI is poured in glass mold, 25 h are dried in vacuo at 80 DEG C, obtains PBI film；It will
PBI film is immersed in 60 h in 60 DEG C of phosphoric acid, takes out and in 80 DEG C of dry 24 h, is denoted as traditional PBI composite membrane；Wherein, PBI
N-Methyl pyrrolidone solution in the mass fraction of PBI be 2%, the concentration of phosphoric acid is 70 wt%.
To there is the cross-linking type polybenzimidazoles high temperature proton exchange of the high conductivity of high antioxygenic property made from embodiment 2
Film and tradition PBI composite membrane, test the battery performance under its different temperatures on monocell evaluating apparatus.Wherein, battery cathode
Nickel (Ni) catalyst is carried using carbon (C) and PBI solution is applied on carbon paper after mixing and is made (using patent
Preparation method disclosed in CN02127802.4), Ni accounts for the quality that the mass percent of C/Ni catalyst is 40%, C/Ni and PBI
Than for 1:1；Anode carries platinum (Pt) catalyst using carbon (C) and is applied on carbon paper obtained (adopt after mixing with PBI solution
The preparation method disclosed in patent CN02127802.4), the mass percent that Pt accounts for C/ Pt catalyst is 70%, Pt in anode
Carrying capacity is 0.5 mg/cm2；Battery operating environment is set separately are as follows: battery temperature is 150 DEG C；Hydrogen and oxygen gas flow rate are respectively
50 mL/min, 100 mL/min, gas are 0.05 MPa without humidification, pressure, and test results are shown in figure 2.
Figure it is seen that the cross-linking type polybenzimidazoles obtained with the high conductivity of high antioxygenic property of embodiment 2
High temperature proton exchange film, due to the promotion of conductivity, reduces the reaction internal resistance of battery compared with traditional PBI composite membrane, so that
Cell discharge performance also significantly increases, and maximum power density is up to 1000 mW/cm2。
Embodiment 3
A kind of preparation side of the cross-linking type polybenzimidazoles high temperature proton exchange film with the high conductivity of high antioxygenic property
Method, comprising the following steps:
(1) by 0.8 g1- vinyl -1,2,4- triazole is dissolved in 10 mL N-Methyl pyrrolidone solvents, is added
Chain initiator azodiisobutyronitrile, wherein the mass content of chain initiator is the 30% of high boiling solvent, is put into oil bath, is reacted
36 h, reaction temperature are 70 DEG C；
(2) it will be added 0.5 g polybenzimidazoles in solution, after stirring and dissolving, add vinyl phosphonic acid, stirring and dissolving
Afterwards, azodiisobutyronitrile is added, 1.5 h, nitrogen protection are stirred at room temperature, gas flow is 100 mL/min；
(3) solution is put into oil bath, is stirred at 80 DEG C, react 24 h；
(4) 5 mL N-Methyl pyrrolidone solvents will be continuously added in solution, after stirring 30 min, free radical are added and quenches
Go out agent ceria, and 30 min are stirred by ultrasonic, pours into casting film plate, is evaporated solvent at 65 DEG C, and obtained high temperature proton is handed over
It changes film carefully to take off, immersion is washed in ethanol, rear dry；
(5) the cross-linking type high temperature proton exchange film after drying is immersed in phosphoric acid solution, 42 h is impregnated at 100 DEG C, after
It takes out, obtains high temperature proton exchange film.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, ability
Other modifications or equivalent replacement that domain those of ordinary skill makes technical solution of the present invention, without departing from skill of the present invention
The spirit and scope of art scheme, are intended to be within the scope of the claims of the invention.
Claims (6)
1. a kind of preparation method of the cross-linking type polybenzimidazoles high temperature proton exchange film with the high conductivity of high antioxygenic property,
Characterized by comprising the following steps:
(1) by 0.5 ~ 2 g1- vinyl -1,2,4- triazole is dissolved in 10 ~ 20 mL high boiling solvents, adds chain initiator
Azodiisobutyronitrile, wherein the mass content of chain initiator is the 20% ~ 50% of high boiling solvent, is put into oil bath, reaction 24 ~ 48
H, reaction temperature are 50 ~ 80 DEG C, obtain solution；
(2) 0.2 ~ 1 g polybenzimidazoles will be added in solution obtained in (1), after stirring and dissolving, add vinyl phosphonic acid,
After stirring and dissolving, azodiisobutyronitrile is added, 1 ~ 2 h, nitrogen protection is stirred at room temperature, gas flow is 100 mL/min, is obtained
Solution；
(3) solution obtained in (2) is put into oil bath, is stirred at 50 ~ 100 DEG C, reacted 12 ~ 48 h, obtain solution；
(4) 5 ~ 10 mL high boiling solvents will be continuously added in solution obtained in (3), after stirring 30 min, free radical are added and quenches
It goes out agent, 30 min is stirred by ultrasonic, pours into casting film plate, is evaporated solvent at 60 ~ 80 DEG C, the high temperature proton exchange film that will be obtained
It carefully takes off, impregnates dry after washing in ethanol；
(5) the cross-linking type high temperature proton exchange film after drying is immersed in phosphoric acid solution, 24 ~ 48 h is impregnated at 60 ~ 120 DEG C
After take out, obtain high temperature proton exchange film.
2. a kind of cross-linking type polybenzimidazoles high temperature matter with the high conductivity of high antioxygenic property according to claim 1
The preparation method of proton exchange, it is characterised in that: the additional amount of vinyl phosphonic acid described in step (1), (2) is 1- ethylene
The 100% ~ 300% of base -1,2,4- triazole molal weight；The additional amount of azodiisobutyronitrile is three nitrogen of 1- vinyl -1,2,4-
The 1% ~ 5% of azoles molal weight.
3. a kind of cross-linking type polybenzimidazoles high temperature matter with the high conductivity of high antioxygenic property according to claim 1
The preparation method of proton exchange, it is characterised in that: high boiling solvent described in step (1), (4) be n,N-dimethylacetamide or
N-Methyl pyrrolidone.
4. a kind of cross-linking type polybenzimidazoles high temperature matter with the high conductivity of high antioxygenic property according to claim 1
The preparation method of proton exchange, it is characterised in that: the free radical quencher is ceria, silica, manganese dioxide
One kind, additional amount be polybenzimidazoles quality 0.1% ~ 0.9%.
5. a kind of cross-linking type polybenzimidazoles high temperature matter with the high conductivity of high antioxygenic property according to claim 1
The preparation method of proton exchange, it is characterised in that: the mass fraction of phosphoric acid is 50% ~ 85% in phosphoric acid solution described in step (5).
6. a kind of cross-linking type polybenzimidazoles high temperature proton exchange film with the high conductivity of high antioxygenic property, feature exist
In: the cross-linking type polybenzimidazoles high temperature proton exchange film with the high conductivity of high antioxygenic property is to pass through claim
What method described in any one of 1 to 5 claim was prepared.
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| CN107556247B (en) * | 2017-08-28 | 2020-07-31 | 吉林大学 | Functional cross-linking agent, preparation method and high-phosphoric-acid-doped cross-linked polybenzimidazole film prepared from functional cross-linking agent |
| CN111205640B (en) * | 2020-01-11 | 2022-07-26 | 山东理工大学 | Preparation method of cyclotriphosphazene hexaphosphate doped polybenzimidazole proton exchange membrane |
| CN111205641B (en) * | 2020-01-11 | 2022-07-26 | 山东理工大学 | Preparation method of tripolycyanogen-ring-containing triphosphonate-doped PBI high-temperature proton exchange membrane |
| CN111349239B (en) * | 2020-03-06 | 2023-01-06 | 珠海冠宇电池股份有限公司 | Proton exchange membrane containing phosphonated hyperbranched polybenzimidazole and preparation method and application thereof |
| CN117721498B (en) * | 2024-02-07 | 2024-05-07 | 宁波中科氢易膜科技有限公司 | Preparation method of organic-inorganic hybrid ion composite membrane |
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| CN105895943A (en) * | 2016-05-03 | 2016-08-24 | 武汉理工大学 | Phosphonic acid-grafted polybenzimidazole high-temperature proton exchange membrane and preparation method thereof |
| CN106750441A (en) * | 2016-12-07 | 2017-05-31 | 黄河科技学院 | A kind of poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film and preparation method thereof |
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| 《Proton Exchange Membrane Developed from Novel Blends of Polybenzimidazole and Poly(vinyl-1,2,4-triazole)》;Mousumi Hazarika 等;《ACS Applied Materials & Interfaces》;20120906;第4卷;第5256-5265页 |
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