CN106549171A - A kind of cross-linking type polybenzimidazoles high temperature proton exchange film with high antioxygenic property high conductivity and preparation method thereof - Google Patents
A kind of cross-linking type polybenzimidazoles high temperature proton exchange film with high antioxygenic property high conductivity and preparation method thereof 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 with high antioxygenic property high conductivity and preparation method thereof, described cross linking membrane is with polybenzimidazoles as polymer backbone, by polymerisation, it is crosslinking agent using vinyl phosphonate and vinyl triazole, the network structure of crosslinking is formed in film, and the free radical quencher for improving film antioxygenic property is doped with film, prepare the high temperature proton exchange film with high conductivity with high antioxygenic property.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, the phosphoric acid losing issue of polybenzimidazoles/phosphoric acid film is solved thoroughly, and the bottleneck that polymer film is attacked by free radical and degraded, use as PEM in can apply to high temperature proton exchange film fuel cell, direct alcohol fuel cell, electrochemical sensor or other electrochemical appliances.
Description
Technical field
The invention belongs to fuel cell material technical field, and in particular to a kind of with high antioxygenic property high conductivity
Cross-linking type polybenzimidazoles high temperature proton exchange film and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells（PEMFC）It is a kind of efficient, cleaning, eco-friendly TRT, is electronic vapour
The ideal power source of car, can act also as disperseing the Military Powers or compact power etc. such as power station, submarine and spacecraft, with very
Wide application prospect.But it is now widely used be perfluor type sulfonic acid membrane cell with Nafion as representative, but
The proton conducting ability of this kind of PEM is affected greatly 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.As PEMFC is limited by operating temperature so that it faces CO tolerances in practical application
The problems such as difference, hydro-thermal difficult management of system.Therefore PEMFC running temperatures are brought up to into more than 100 DEG C, just can effectively gram
The problems referred to above of clothes tradition Nafion base PEMFC, the fuel cell of this type（FC）Normally referred to as high temperature proton exchange film
Fuel cell（HT-PEMFC）, it is an important developing direction of PEMFC technologies.
HT-PEMFC systems have the following advantages：1）Electrochemical reaction speed is improved, and effectively reduces electrochemical cathode polarization
Overpotential, it is allowed to reduce catalyst load amount, it is allowed to use non-platinum catalyst；2）The humidification requirements of reacting gas are reduced；3）Electricity
Pool inner water simplifies hydro-thermal management with gas phase presence；Additionally, HT-PEMFC simplifies FC cooling systems to a certain extent.In view of
HT-PEMFC tempting development prospect, has extensively carried out the development of HT-PEMFC critical materials 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 focus it
One.
At present for the research of HT-PEMFC PEMs is concentrated mainly on polybenzimidazoles（PBI）On, it is in 1959
Year is reported in United States Patent (USP) first, and PBI film products are introduced to the market by Hoechst Celanese companies of the U.S. within 1988.Such as
The present, PBI as polymer-based material the most outstanding in engineering thermoplasties, in the high temperature proton exchange as HT-PEMFC
Huge validity and feasibility are shown in terms of film.But PBI types membrane material is in hot operation（T≥150℃）, meeting can not
There is degraded with avoiding.
Research finds that in fuel cell operation, oxygen penetrates into anode-side through film, in anode Pt and micro transition
Under the catalytic action of metal ion, the free radical such as formation OH and HOO, the nitrogen-containing group on OH free radical attack PBI main chains,
The C-H bond that HOO free radicals are attacked on phenyl ring, makes PBI backbone breakings；High-temperature oxidation environment is also easy to make on PBI main chains simultaneously
The oxidation of two Amino End Groups, there is decarboxylic reaction and produce phenylene free radical in end carboxyl.These free radicals for producing can aggravate PBI
The degraded of film, causes battery performance to decline to a great extent.Room Jian Hua etc. adopts epoxides（CN 200710171866.9）, dihalo-（It is many
Halogen）Alkane（CN 200710171865.4）And maleic anhydride（CN 200710171867.3）To an end ammonia on PBI main chains
Base carries out crosslinking protection, so as to slow down the degraded of film；Li Zhongfang et al. adopts urea（CN 101768270 A）, 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 that thing structure can be produced during HT-PEMFC runnings are effectively quenched, so as to slow down the degraded of PBI films.
In sum, obtain such PEM polymeric substrates at present easily to be attacked and the difficult problem such as degraded by free radical
Its business-like application is restricted, and by adding free radical quencher in film, cross-linked structure being built in film, effectively can be kept away
Exempt from free radical to attack and degrade, lift the service life of film, and improve the dimensional stability of film.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of with high antioxygenic property high conductivity
Cross-linking type polybenzimidazoles high temperature proton exchange film and preparation method thereof, by with polybenzimidazoles as polymer backbone, passing through
Polymerisation, is crosslinking agent using vinyl phosphonate and vinyl triazole, the network structure of crosslinking is formed in film, and in film
In be doped with the free radical quencher for improving film antioxygenic property, prepare the high temperature with high antioxygenic property and high conductivity
PEM.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, the phosphoric acid for thoroughly solving polybenzimidazoles/phosphoric acid film is lost in
Problem, and the bottleneck that polymer backbone is attacked by free radical and degraded.
To achieve these goals, the technical solution used in the present invention is：
A kind of preparation method of the cross-linking type polybenzimidazoles high temperature proton exchange film with high antioxygenic property high conductivity, bag
Include following steps：
（1）By 0.5 ~ 2 g1- vinyl -1,2,4- triazoles are dissolved in 10 ~ 20 mL high boiling solvents, add chain initiator
The mass content of azodiisobutyronitrile, wherein chain initiator is the 20 ~ 50% of high boiling solvent, is put in 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 phosphonate, after stirring and dissolving,
Azodiisobutyronitrile is added, 1 ~ 2 h is stirred at room temperature, nitrogen protection, gas flow are 100 mL/min；
（3）Solution is put in 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, after 30 min of stirring, adds free radical quencher, ultrasound to stir
30 min are mixed, is poured in casting film plate, solvent is evaporated at 60 ~ 80 DEG C, the high temperature proton exchange film for obtaining carefully is taken off, soaked
Bubble in ethanol, is dried after washing；
（5）Dried cross-linking type high temperature proton exchange film is immersed in phosphoric acid solution, 24 ~ 48 h at 60 ~ 120 DEG C, are impregnated
After take out, obtain high temperature proton exchange film.
Preferably, step（2）Described in vinyl phosphonate addition be 1- vinyl -1,2,4- triazole mole matter
The 100% ~ 300% of amount；The addition of azodiisobutyronitrile for 1- vinyl -1,2,4- triazole molal weights 1 ~ 5%；
Preferably, step（1）、（4）Described in high boiling solvent be DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.
Preferably, described free radical quencher be ceria, silica, one kind of manganese dioxide, its addition
For the 0.1% ~ 0.9% of polybenzimidazoles quality；
Preferably, step（5）Described in phosphoric acid solution the mass fraction of phosphoric acid be 50% ~ 85%.
The cross-linking type polybenzimidazoles high temperature with high antioxygenic property high conductivity obtained using above-mentioned preparation method
PEM.
The cross-linking type polybenzimidazoles high temperature proton exchange film with high antioxygenic property high conductivity that the present invention is provided
And preparation method thereof, have the advantages that compared with prior art：
1. it is polymer backbone that the present invention is respectively adopted polybenzimidazoles, by polymerisation, using vinyl phosphonate and ethene
Base triazole is crosslinking agent, and the network structure of crosslinking is formed in film, and raising film antioxygenic property is doped with film
Free radical quencher, uniform by structure of composite membrane obtained in self-crosslinking, it is adaptable to anhydrous system, 120 ~ 200 DEG C of operating temperature
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, the phosphoric acid for thoroughly solving polybenzimidazoles/phosphoric acid film is lost in
Problem, and the bottleneck that polymer estimation is attacked by free radical and degraded.
3. the polyvinylphosphonic acid and triazole in crosslinking agent of the present invention, can effectively adsorb phosphoric acid molecules,
Improve the long-time stability of film electrical conductivity in cell operation.
4. the cross-linking type polybenzimidazoles high temperature proton exchange with high antioxygenic property high conductivity proposed by the present invention
Film can apply to high temperature proton exchange film fuel cell, direct alcohol fuel cell, electrochemical sensor or other electrochemistry
Use as PEM in device.
Description of the drawings
Fig. 1 is the 1 obtained cross-linking type polybenzimidazoles high temperature proton with high antioxygenic property high conductivity of embodiment
The electrical conductivity variation with temperature figure of exchange membrane and tradition PBI composite membranes；
Fig. 2 is the 2 obtained cross-linking type polybenzimidazoles high temperature proton exchange with high antioxygenic property high conductivity of embodiment
The cell polarization curves figure of film and tradition PBI composite membranes.
Specific embodiment
Polybenzimidazoles used in example below（PBI, CAS: 25928-81-8）Purchased from FuMA-Tech companies；N,N-
Dimethyl acetamide（DMAC, CAS: 127-19-5）, 1-METHYLPYRROLIDONE（NMP, CAS: 872-50-4）Purchased from Tianjin
Great Mao chemical reagents corporations；1- vinyl -1,2,4- triazoles（CAS: 2764-83-2）It is limited purchased from Shanghai source leaf biotechnology
Company；Azodiisobutyronitrile（AIBN, CAS: 78-67-1）Purchased from Tianjin great Mao chemical reagents corporations；Vinyl phosphonate
(CAS:1746-03-8) purchased from Chengdu Hua Xia chemical reagent Co., Ltd；Ceria, manganese dioxide, silica, phosphoric acid
Purchased from Shanghai Aladdin biochemical technology limited company.
Embodiment 1
A kind of preparation method of the cross-linking type polybenzimidazoles high temperature proton exchange film with high antioxygenic property high conductivity, bag
Include following steps：
（1）By 2 g1- vinyl -1,2,4- triazoles are dissolved in 20 mL 1-METHYLPYRROLIDONEs, add chain initiator idol
The mass content of nitrogen bis-isobutyronitrile, wherein chain initiator for high boiling solvent 25%；It is put in oil bath, reacts 48 h, reaction temperature
Spend for 50 DEG C；
（2）1 g polybenzimidazoles will be added in solution, after stirring and dissolving, vinyl phosphonate is added, after stirring and dissolving, is added
Azodiisobutyronitrile, is stirred at room temperature 2 h, and nitrogen protection, gas flow are 100 mL/min；
（3）Solution is put in oil bath, is stirred at 100 DEG C, react 48 h；
（4）To continue plus 10 mL 1-METHYLPYRROLIDONEs in solution, after 30 min of stirring, add free radical quencher titanium dioxide
Manganese, 30 min of ultrasonic agitation are poured in casting film plate, at 80 DEG C are evaporated solvent, the high temperature proton exchange film for obtaining carefully is taken off
Under, immersion in ethanol, is dried after washing；
（5）Dried cross-linking type high temperature proton exchange film is immersed in phosphoric acid solution, is taken out after 48 h are impregnated at 120 DEG C,
Obtain high temperature proton exchange film.
In order to hand over the cross-linking type polybenzimidazoles high temperature proton with high antioxygenic property high conductivity obtained above
Change film to be contrasted, adopt solution casting method to prepare thickness for 50 μm of PBI films, then impregnation of phosphoric acid, PBI/ phosphoric acid films are obtained,
Specifically preparation process is：The 1-METHYLPYRROLIDONE solution of PBI is poured in glass mold, 25 h is vacuum dried at 80 DEG C,
Obtain PBI films；PBI films are immersed in into 60 h in 60 DEG C of phosphoric acid, are taken out and in 80 DEG C of 24 h of drying, be denoted as traditional PBI multiple
Close film；Wherein, in the 1-METHYLPYRROLIDONE solution of PBI, the mass fraction of PBI is 2%, and the concentration of phosphoric acid is 70 wt%.
The 1 obtained cross-linking type polybenzimidazoles high temperature proton exchange film with high antioxygenic property high conductivity of embodiment
And tradition PBI composite membranes, testing conductivity variation with temperature figure.There is the high electricity of high antioxygenic property by embodiment 1 obtained
The cross-linking type polybenzimidazoles high temperature proton exchange film and tradition PBI composite membranes of conductance is cut into size for 40 mm × 10 mm's
Rectangular sheet, then by the 1 obtained cross-linking type polybenzimidazoles high temperature proton with high antioxygenic property high conductivity of embodiment
Exchange membrane and tradition PBI composite membranes are respectively placed in electrical conductivity fixture, and fixture is put in vacuum drying chamber, are protected at 90 DEG C
3 h are held, then temperature rises to 170 DEG C from 90 DEG C, the electrical 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 1 obtained cross-linking type polybenzimidazoles with high antioxygenic property high conductivity of embodiment
Compared with traditional PBI composite membranes, electrical conductivity is substantially improved high temperature proton exchange film, and this is as in cross-linked structure, triazole is deposited
, there is provided more phosphate adsorption sites, so as to improve the electrical conductivity of film.
Embodiment 2
A kind of preparation method of the cross-linking type polybenzimidazoles high temperature proton exchange film with high antioxygenic property high conductivity, bag
Include following steps：
（1）By 1.5 g1- vinyl -1,2,4- triazoles are dissolved in 15 mL 1-METHYLPYRROLIDONE solvents, are added chain and are drawn
Agent azodiisobutyronitrile is sent out, the wherein mass content of chain initiator is the 38% of high boiling solvent, is put in oil bath, reacts 28 h,
Reaction temperature is 80 DEG C；
（2）0.8 g polybenzimidazoles will be added in solution, after stirring and dissolving, vinyl phosphonate is added, after stirring and dissolving, plus
Enter azodiisobutyronitrile, 2 h are stirred at room temperature, nitrogen protection, gas flow are 100 mL/min；
（3）Solution is put in oil bath, is stirred at 50 DEG C, react 48 h；
（4）8 mL 1-METHYLPYRROLIDONE solvents will be continuously added in solution, after 30 min of stirring, free radical quencher is added
Ceria, 30 min of ultrasonic agitation are poured in casting film plate, at 70 DEG C are evaporated solvent, by the high temperature proton exchange film for obtaining
Carefully take off, immersion in ethanol, is dried after washing；
（5）Dried cross-linking type high temperature proton exchange film is immersed in phosphoric acid solution, 24 h is impregnated at 80 DEG C, is taken out afterwards,
Obtain high temperature proton exchange film.
In order to be contrasted with cross-linking type polybenzimidazoles obtained above/polyethylene triazole high temperature proton exchange film,
Solution casting method is adopted to prepare thickness for 50 μm of PBI films, then impregnation of phosphoric acid, PBI/ phosphoric acid films, concrete preparation process is obtained
For：The 1-METHYLPYRROLIDONE solution of PBI is poured in glass mold, 25 h are vacuum dried at 80 DEG C, obtain PBI films；Will
PBI films are immersed in 60 h in 60 DEG C of phosphoric acid, take out and in 80 DEG C of 24 h of drying, are denoted as traditional PBI composite membranes；Wherein, PBI
1-METHYLPYRROLIDONE solution in the mass fraction of PBI be 2%, the concentration of phosphoric acid is 70 wt%.
By the 2 obtained cross-linking type polybenzimidazoles high temperature proton exchange with high antioxygenic property high conductivity of embodiment
Film and tradition PBI composite membranes, the battery performance tested under its different temperatures on monocell evaluating apparatus.Wherein, GND
Using carbon（C）Carry nickel（Ni）Catalyst is applied in after being well mixed with PBI solution on carbon paper and is obtained（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 adopts carbon（C）Carry platinum（Pt）Catalyst is applied in after being well mixed with PBI solution on carbon paper and is obtained（Adopt
With the preparation method disclosed in patent CN02127802.4）, it is 70% that Pt accounts for the mass percent of C/ Pt catalyst, Pt in positive pole
Carrying capacity is 0.5 mg/cm2；Battery operating environment is respectively set as：Battery temperature is 150 DEG C；Hydrogen and oxygen gas flow rate are respectively
50 mL/min, 100 mL/min, without humidification, pressure is 0.05 MPa to gas, and test result is as shown in Figure 2.
Figure it is seen that the 2 obtained cross-linking type polybenzimidazoles with high antioxygenic property high conductivity of embodiment
High temperature proton exchange film due to the lifting of electrical conductivity, reduces the reaction internal resistance of battery compared with traditional PBI composite membranes so that
Cell discharge performance is also significantly increased, and maximum power density is up to 1000 mW/cm2。
Embodiment 3
A kind of preparation method of the cross-linking type polybenzimidazoles high temperature proton exchange film with high antioxygenic property high conductivity, bag
Include following steps：
（1）By 0.8 g1- vinyl -1,2,4- triazoles are dissolved in 10 mL 1-METHYLPYRROLIDONE solvents, are added chain and are drawn
Agent azodiisobutyronitrile is sent out, the wherein mass content of chain initiator is the 30% of high boiling solvent, is put in oil bath, reacts 36 h,
Reaction temperature is 70 DEG C；
（2）0.5 g polybenzimidazoles will be added in solution, after stirring and dissolving, vinyl phosphonate is added, after stirring and dissolving, plus
Enter azodiisobutyronitrile, 1.5 h are stirred at room temperature, nitrogen protection, gas flow are 100 mL/min；
（3）Solution is put in oil bath, is stirred at 80 DEG C, react 24 h；
（4）5 mL 1-METHYLPYRROLIDONE solvents will be continuously added in solution, after 30 min of stirring, free radical quencher is added
Ceria, 30 min of ultrasonic agitation are poured in casting film plate, at 65 DEG C are evaporated solvent, by the high temperature proton exchange film for obtaining
Carefully take off, immersion is washed in ethanol, is dried afterwards；
（5）Dried cross-linking type high temperature proton exchange film is immersed in phosphoric acid solution, 42 h at 100 DEG C, are impregnated, after take
Go out, obtain high temperature proton exchange film.
The above, the only specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, ability
Other modifications or equivalent that domain those of ordinary skill is made to technical scheme, without departing from skill of the present invention
The spirit and scope of art scheme, all should cover in the middle of scope of the presently claimed invention.
Claims (6)
1. a kind of preparation method of the cross-linking type polybenzimidazoles high temperature proton exchange film with high antioxygenic property high conductivity,
Characterized in that, comprising the following steps：
（1）By 0.5 ~ 2 g1- vinyl -1,2,4- triazoles are dissolved in 10 ~ 20 mL high boiling solvents, add chain initiator
The mass content of azodiisobutyronitrile, wherein chain initiator is the 20% ~ 50% of high boiling solvent, is put in 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 phosphonate, after stirring and dissolving,
Azodiisobutyronitrile is added, 1 ~ 2 h is stirred at room temperature, nitrogen protection, gas flow are 100 mL/min；
（3）Solution is put in 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, after 30 min of stirring, adds free radical quencher, ultrasound to stir
30 min are mixed, is poured in casting film plate, solvent is evaporated at 60 ~ 80 DEG C, the high temperature proton exchange film for obtaining carefully is taken off, soaked
Bubble is dried after washing in ethanol；
（5）Dried cross-linking type high temperature proton exchange film is immersed in phosphoric acid solution, 24 ~ 48 h at 60 ~ 120 DEG C, are impregnated
After take out, obtain high temperature proton exchange film.
2. a kind of cross-linking type polybenzimidazoles high temperature matter with high antioxygenic property high conductivity according to claim 1
The preparation method of proton exchange, it is characterised in that：Step（1）、（2）Described in vinyl phosphonate addition be 1- ethene
The 100% ~ 300% of base -1,2,4- triazole molal weights；The addition 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 high antioxygenic property high conductivity according to claim 1
The preparation method of proton exchange, it is characterised in that：Step（1）、（4）Described in high boiling solvent be DMAC N,N' dimethyl acetamide or
1-METHYLPYRROLIDONE.
4. a kind of cross-linking type polybenzimidazoles high temperature matter with high antioxygenic property high conductivity according to claim 1
Proton exchange and preparation method thereof, it is characterised in that：Described free radical quencher is ceria, silica, titanium dioxide
One kind of manganese, its addition for polybenzimidazoles quality 0.1% ~ 0.9%.
5. a kind of cross-linking type polybenzimidazoles high temperature matter with high antioxygenic property high conductivity according to claim 1
Proton exchange and preparation method thereof, it is characterised in that：Step（5）Described in phosphoric acid solution the mass fraction of phosphoric acid be 50% ~
85%。
6. a kind of cross-linking type polybenzimidazoles high temperature proton exchange film with high antioxygenic property high conductivity, its feature exist
In：The cross-linking type polybenzimidazoles high temperature proton exchange film with high antioxygenic property high conductivity is by claim
What the method described in 1 to 5 any one claim was prepared.
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|---|---|---|---|---|
| CN107556247A (en) * | 2017-08-28 | 2018-01-09 | 吉林大学 | A kind of functional form crosslinking agent, preparation method and the phosphate-doped cross-linking type polybenzimidazoles film of height prepared therefrom |
| CN111205640A (en) * | 2020-01-11 | 2020-05-29 | 山东理工大学 | Preparation of cyclotriphosphazene hexaphosphate doped polybenzimidazole proton exchange membrane |
| CN111205641A (en) * | 2020-01-11 | 2020-05-29 | 山东理工大学 | Preparation of tripolycyanogen ring-containing triphosphonate-doped PBI high-temperature proton exchange membrane |
| CN111349239A (en) * | 2020-03-06 | 2020-06-30 | 珠海冠宇电池有限公司 | Proton exchange membrane containing phosphonated hyperbranched polybenzimidazole and preparation method and application thereof |
| CN117721498A (en) * | 2024-02-07 | 2024-03-19 | 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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| CN107556247A (en) * | 2017-08-28 | 2018-01-09 | 吉林大学 | A kind of functional form crosslinking agent, preparation method and the phosphate-doped cross-linking type polybenzimidazoles film of height prepared therefrom |
| 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 |
| CN111205640A (en) * | 2020-01-11 | 2020-05-29 | 山东理工大学 | Preparation of cyclotriphosphazene hexaphosphate doped polybenzimidazole proton exchange membrane |
| CN111205641A (en) * | 2020-01-11 | 2020-05-29 | 山东理工大学 | Preparation of tripolycyanogen ring-containing triphosphonate-doped PBI high-temperature proton exchange membrane |
| CN111349239A (en) * | 2020-03-06 | 2020-06-30 | 珠海冠宇电池有限公司 | Proton exchange membrane containing phosphonated hyperbranched polybenzimidazole and preparation method and application thereof |
| 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 |
| CN117721498A (en) * | 2024-02-07 | 2024-03-19 | 宁波中科氢易膜科技有限公司 | Preparation method of organic-inorganic hybrid ion composite membrane |
| 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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