CN103554537B - A kind of film and preparation method thereof - Google Patents

A kind of film and preparation method thereof Download PDF

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Publication number
CN103554537B
CN103554537B CN201310530700.7A CN201310530700A CN103554537B CN 103554537 B CN103554537 B CN 103554537B CN 201310530700 A CN201310530700 A CN 201310530700A CN 103554537 B CN103554537 B CN 103554537B
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film
mixture
kynoar
mixed liquor
mesoporous
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CN103554537A (en
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沈杭燕
郭冰
王雪丹
杨乐斌
刘薇
舒康颖
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China Jiliang University
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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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention provides a kind of film and preparation method thereof, preparation method comprises the following steps: by CsHSO4With mesoporous Al2O3It is mixed to get mixture；Described mixture is become mixed liquor with Kynoar solution mixing system；And use coating process that prepared by described mixed liquor film forming.Preparing film not only low cost by this method, be prone to film forming, and when as PEM, have high conductivity 100 200 DEG C of scopes, electrical conductivity increases to 10‑3S cm 1, its proton conductivity at 200 DEG C up to 2.5 × 10‑3S cm 1, resistance alcohol rate is high about 3 orders of magnitude than Nafion.

Description

A kind of film and preparation method thereof
Technical field
The present invention relates to a kind of film, in particular to a kind of inorganic-organic PEM and preparation method thereof.
Background technology
Have been developed over various film, such as, reverse osmosis membrane (0.0001～0.005 μm), NF membrane up to now (0.001～0.005 μm), ultrafilter membrane (0.001～0.1 μm), micro-filtration membrane (0.1～1 μm), electrodialytic membranes, Pervaporation membrane, liquid Body film, gas separation membrane, electrode film, PEM etc..The separating mechanism that their correspondence is different, different equipment, there is difference Application.Film itself can be made up of polymer, inorganic material or liquid, and its structure can be homogenously or inhomogenously, Porous or atresia, solid or liquid, charged or neutrality.The thickness of film can be as thin as several micron, thick to several millis Rice.Different films has different microstructures and function, needs to prepare by different methods.Film-forming method is always film field Core research topic, the core technology that Ye Shige company holds in close confidence.Wherein, PEM (Proton Exchange Membrane Fuel, PEM) it is the core component of PEMFC, the barrier film used in PEM and general electrochmical power source is had any different.Proton Exchange film fuel battery has become the clean of gasoline internal combustion mechanomotive force most competitiveness and has replaced power source.
It is known that energy problem is constantly subjected to global concern, taps a new source of energy and have become as every country development A major part.Fuel cell is owing to having advantages such as energy conversion efficiency is high, environmental pollution is little and each by the world The most attention of state.Fuel cell has many types, wherein Proton Exchange Membrane Fuel Cells (Polymer Exchange Membrane Fuel Cell, PEMFC) there is started quickly at low temperature, specific energy height, noiselessness, the plurality of advantages such as pollution-free, quilt As electric automobile and the preferable energy of movable small electric power system, the uninterrupted power source of electronic equipment, decentralized power station, boat It and military equipment power supply, public place emergency power supply etc., its wide application prospect is just becoming the study hotspot of countries in the world One of.On the basis of PEMFC, replace pure hydrogen directly as fuel with methanol, system, this fuel cell can be greatly simplified It is referred to as DMFC (Direct Methanol Fuel Cell, DMFC).DMFC have volume little, lightweight, combustion The advantages such as material abundance, low price, storage are easy to carry, are preferable car power sources.
PEM (Proton exchange membrane, PEM) is Proton Exchange Membrane Fuel Cells (Proton Exchange membrane fuel cell, PEMFC) and the core of direct alcohol fuel cell (including DMFC and DEFC) One of part, its effect is: (1) separates anode and negative electrode, stops fuel and air (oxygen) directly to mix generation chemical reaction； (2) proton conducting, proton conductivity is the highest, and the internal resistance of film is the least, and the efficiency of fuel cell is the highest；(3) electrical insulator, stops electricity Son conducts in film, and electronics by outside line road direction cathode flow, is produced foreign current for people to use by anode.Generally, fuel Battery PEM material must is fulfilled for claimed below: (1) low cost；(2) high proton conductivity；(3) good mechanical strength is (anti- Swelling) and dimensional stability；(4) excellent chemical stability and electrochemical stability；(5) the lowest gas or methanol crossover Rate；(6) mate with catalyst layer；(7) life-time service is stable.The performance of PEM will directly affect PEMFC's Yu DMFC Battery performance, energy conversion efficiency and service life.
At present, using most PEMs is the Nafion membrane that du pont company produces, and has low-temperature protonic and leads The advantage that electricity rate is high and chemical stability is good.But it there are still some shortcomings: 1) this film depends strongly on water and is situated between for conduction Matter, when operating temperature is more than 100 DEG C, owing in film, moisture evaporation causes proton conduction property drastically to decline, can only be at low temperature (80 DEG C) below, high humility (40%RH) used above.At present, assemble the widely used Nafion membrane of PEMFC Yu DMFC, therefore need Additional huge humidifying equipment is wanted to reduce battery temperature；2), when working at a temperature of below 80 DEG C, there is serious CO pair The poisoning problem of catalyst, and for DMFC, the selection to first alcohol and water is poor by property, and alcohol-rejecting ability is poor, is using Time more than 40% methanol can pass through this film, this reduces battery performance and fuel availability, be not suitable for use in direct methanol The PEM of fuel cell (Directmethanol fuel cell, DMFC), methanol is by caused by the infiltration of Nafion membrane simultaneously Anode performance decay be limit DMFC development subject matter.Therefore, Nafion this series difficult problem caused enable for Higher temperature (T > 100 DEG C), the resistance high novel proton exchange membranes of alcohol rate developmental research imperative.
Summary of the invention
For the film proton conductivity in the case of operating temperature is more than 100 DEG C used in fuel cell in prior art Relatively low problem, the invention provides a kind of film with high conductivity and preparation method thereof under middle low temperature.
According to an aspect of the invention, it is provided a kind of preparation method preparing film, the method comprises the following steps:
A) by CsHSO4With mesoporous Al2O3It is mixed to get mixture；
B) mixture is become mixed liquor with Kynoar solution mixing system；And
C) use coating process that prepared by mixed liquor film forming.
In step a), by CsHSO4With mesoporous Al2O3The step preparing mixture farther includes: by CsHSO4 With mesoporous Al2O3Mix and obtain mixture；Heat the mixture to 250 DEG C of also constant temperature 12 hours, be cooled to room temperature；And grind Mill mixture 5 minutes；Wherein, CsHSO4With mesoporous Al2O3Mass ratio between 0.75 and 5.81.
In step b), the step of mixed liquor is become to farther include with Kynoar solution mixing system in mixture: Under 50 DEG C-70 DEG C heating and/or stirring condition, Kynoar is mixed with N,N-dimethylacetamide, be prepared as poly-inclined fluorine Vinyl solution, the time wherein stirred is until forming the Kynoar solution of clarification；And shake in stirring and/or ultrasound wave Under the conditions of swinging, preferably under conditions of stirring and supersonic oscillations are used alternatingly continuously, by mixture and Kynoar solution Being mixed to get mixed liquor, wherein, the mass ratio of mixture and Kynoar is between 0.34 and 2.22；And stir time Between be 20-30 minute, the time of supersonic oscillations is 20-30 minute.
In this step, by use PVDF as the filmogen (substrate) of film, owing to PVDF has good thermoplastic Property, make the mechanical performance of composite membrane be improved, the resistance alcohol rate of composite membrane can also be improved simultaneously；And, the price of PVDF is low Honest and clean, can directly reduce the price of film.
Additionally, by mixture is become mixed liquor with Kynoar solution mixing system, make CsHSO4With mesoporous Al2O3Quilt It is uniformly dispersed in Kynoar solution.When low temperature (less than 100 DEG C), mesoporous Al2O3Mesoporous absorption hydrone make For proton conductor, film is made to have higher low-temperature conductivity.At mesophilic range (100 DEG C-200 DEG C), solid acid CsHSO4Make For proton conductor, film can be made to have middle temperature electric conductivity.
In step c), the step using coating process that mixed liquor is prepared film forming farther includes: utilize coating instrument Being coated on substrate by mixed liquor, dry mixed liquid is with produced film；And from substrate, peel off described film.
In above-mentioned steps c), implementing the step of dry mixed liquid in an oven, wherein, the temperature being dried is 50 DEG C-70 DEG C, the time being dried is 3-5 hour；Coating instrument is adjustable spreader, spin coater, automatic coating machine, coating machine；And And substrate can be sheet glass.
Before step a), it is also possible to include preparing mesoporous Al2O3Step, this step includes: by six trichloride hydrate lanthanums It is dissolved in deionized water, makes the second solution, weigh solvent hexamethylene and surfactant, make the 3rd solution, mix second Solution and the 3rd solution, generate the first white gels, adds aluminium secondary butylate, obtains the second white gels；By the second white gels Be transferred in constant temperature oscillator, 60 DEG C, vibrate 24 hours under 180rpm/ minute；By described second white gels after vibration Being transferred in bottle,suction carry out sucking filtration, sucking filtration afterproduct is dried at 100 DEG C, obtains mesoporous aluminum complex powder body；And will be situated between The method roasting of hole aluminum complex powder body temperature programming, the program of roasting is: heat up 4 hours to 500 DEG C from 25 DEG C, 500 At DEG C be incubated 4 hours, from 500 DEG C cooling 2 hours to 25, wherein, the speed of cooling is 1.98 DEG C/min thus obtains mesoporous Al2O3；Wherein, described surfactant is Span80, Span85 or X114.
The film prepared by above-mentioned steps can be as PEM.
According to the second aspect of the invention, a kind of film prepared according to above method is additionally provided, with percentage by weight Meter, the composition of described film includes:
CsHSO4 17.16%-47.37%
Mesoporous Al2O38.16%-22.84%；
Kynoar 31.58%-73.47%；
The film that the present invention provides can be as PEM.
In sum, the present invention use Kynoar (PVDF) as substrate, then by solid peracid CsHSO4Jie of doping Porous aluminum oxide (Al2O3) be doped in Kynoar, the film prepared by this method not only low cost, it is prone to film forming, and Having high conductivity 100-200 DEG C of scope, electrical conductivity increases to 10-3S cm-1, its proton conductivity at 200 DEG C up to 2.5 ×10-3S cm-1, resistance alcohol rate is high about 3 orders of magnitude than Nafion.
Accompanying drawing explanation
Fig. 1 is the photo of the film according to embodiments of the invention 1；
Fig. 2 is that the film according to embodiments of the invention 1 becomes at 25 DEG C-200 DEG C temperature range inner proton conductivity with temperature The curve chart changed；And
Fig. 3 is the correlation curve figure of the film according to embodiments of the invention 2 and the methanol permeability of Nafion membrane.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete Describe, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments wholely.Based on Embodiment in the present invention, the every other embodiment that those of ordinary skill in the art are obtained, broadly fall into present invention protection Scope.
The preparation of embodiment 1 film S1
Take 37.3670g C6H12With 6.2021g X-114(4-(C8H17)C6H4(OCH2CH2)n-OH) mix and blend 15 minutes Generate solution I；Take 0.660g LaCL3·6H2O and 7.992g distilled water mixing and stirring, generates solution II；Solution I and molten Liquid II mixing and stirring, generates white gels I；Take 21.893g Al (C4H9O)3Join in white gels I, stir, Obtain white gels II；White gels II is put in water bath with thermostatic control vibration case, constant temperature 60 DEG C, 180rpm/ minute vibration 24h； By white gels II after vibration, with buchner funnel sucking filtration 1.5h, the white powder obtained puts into baking oven, constant temperature 100 DEG C baking 1440 minutes to remove moisture；Roasting in chamber type electric resistance furnace put into by sample after drying, obtains mesoporous Al2O3Powder sample.Roasting Burning program is: heat up 4 hours to 500 DEG C from 25 DEG C, is incubated 4 hours at 500 DEG C, lowers the temperature 2 hours to 25 DEG C from 500 DEG C.
Take 2.303gCsHSO4Al mesoporous with 3.065g2O3Powder mixes, and heats the mixture to 250 DEG C and constant temperature 12 is little Time, it is cooled to room temperature.Grind 5 minutes, obtain mix powder sample.
Take 3g PVDF(Kynoar) join 25g DMAC(N, N-dimethyl acetylamide) in, it is heated to 50 DEG C, and Use magnetic agitation, until solution clarification, prepare PVDF-DMFC solution.
Taking 2g mix powder and add PVDF-DMFC solution, magnetic agitation 30 minutes and supersonic oscillations 30 minutes are continuously It is used alternatingly, until mesoporous Al2O3Even particulate dispersion in the middle of solution, the white glue of solution.Then, this is uniformly mixed White gum solution slowly pour on smooth surface, clean sheet glass, with adjustable be coated with step instrument be coated onto glass On sheet, being then placed in baking oven, constant temperature 50 DEG C dries 3h；Finally take out sheet glass, scrape thin film with blade, obtain film, the figure of film Sheet is with reference to Fig. 1, and wherein, in this film, by weight percentage, the composition of film includes: CsHSO417.16%；Mesoporous Al2O322.84%；Kynoar 60%.This film can be used as the PEM in fuel cell.
The preparation of embodiment 2 film S2
Take 37.3670g C6H12With 6.2021g X-114(4-(C8H17)C6H4(OCH2CH2)n-OH) mix and blend 15 minutes Generate solution I；Take 0.660g LaCL3·6H2O and 7.992g distilled water mixing and stirring, generates solution II；Solution I and molten Liquid II mixing and stirring, generates white gels I；Take 21.893g Al (C4H9O)3Join in white gels I, stir, Obtain white gels II；White gels II is put in water bath with thermostatic control vibration case, constant temperature 60 DEG C, 180rpm/ minute vibration 24h； By white gels II after vibration, with buchner funnel sucking filtration 1.5h, the white powder obtained puts into baking oven, constant temperature 100 DEG C baking 1440 minutes to remove moisture；Roasting in chamber type electric resistance furnace put into by sample after drying, obtains mesoporous Al2O3Powder sample.Roasting Burning program is: heat up 4 hours to 500 DEG C from 25 DEG C, is incubated 4 hours at 500 DEG C, lowers the temperature 2 hours to 25 DEG C from 500 DEG C.
Take 4.504gCsHSO4Al mesoporous with 2.012g2O3Powder mixes, and heats the mixture to 250 DEG C and constant temperature 12 is little Time, it is cooled to room temperature.Grind 5 minutes, obtain mix powder sample.
Take 1.003g PVDF(Kynoar) join 25g DMAC(N, N-dimethyl acetylamide) in, it is heated to 70 DEG C, and use magnetic agitation, until solution clarification, prepare PVDF-DMFC solution.
Take 0.3611g mix powder and add PVDF-DMFC solution, magnetic agitation 25 minutes and supersonic oscillations 25 minutes It is used alternatingly continuously, until mesoporous Al2O3Even particulate dispersion in the middle of solution, the white glue of solution.Then, this is uniform The white gum solution of mixing slowly pours on smooth surface, clean sheet glass, is coated onto with adjustable step instrument that is coated with On sheet glass, being then placed in baking oven, constant temperature 70 DEG C dries 3h；Finally take out sheet glass, scrape thin film with blade, obtain film, film Picture with reference to Fig. 1, wherein, in this film, by weight percentage, the composition of film includes: CsHSO418.37%；Mesoporous Al2O38.16%；Kynoar 73.47%.This film can be used as the PEM in fuel cell.
The preparation of embodiment 3 film S3
Take 37.3670g C6H12With 6.2021g X-114(4-(C8H17)C6H4(OCH2CH2)n-OH) mix and blend 15 minutes Generate solution I；Take 0.660g LaCL3·6H2O and 7.992g distilled water mixing and stirring, generates solution II；Solution I and molten Liquid II mixing and stirring, generates white gels I；Take 21.893g Al (C4H9O)3Join in white gels I, stir, Obtain white gels II；White gels II is put in water bath with thermostatic control vibration case, constant temperature 60 DEG C, 180rpm/ minute vibration 24h； By white gels II after vibration, with buchner funnel sucking filtration 1.5h, the white powder obtained puts into baking oven, constant temperature 100 DEG C baking 1440 minutes to remove moisture；Roasting in chamber type electric resistance furnace put into by sample after drying, obtains mesoporous Al2O3Powder sample.Roasting Burning program is: heat up 4 hours to 500 DEG C from 25 DEG C, is incubated 4 hours at 500 DEG C, lowers the temperature 2 hours to 25 DEG C from 500 DEG C.
Take 4.504gCsHSO4Al mesoporous with 2.012g2O3Powder mixes, and heats the mixture to 250 DEG C and constant temperature 12 is little Time, it is cooled to room temperature.Grind 5 minutes, obtain mix powder sample.
Take 1.003g PVDF(Kynoar) join 25g DMAC(N, N-dimethyl acetylamide) in, it is heated to 70 DEG C, and use magnetic agitation, until solution clarification, prepare PVDF-DMFC solution.
Take 2.1667g mix powder and add PVDF-DMFC solution, magnetic agitation 20 minutes and supersonic oscillations 20 minutes It is used alternatingly continuously, until mesoporous Al2O3Even particulate dispersion in the middle of solution, the white glue of solution.Then, this is uniform The white gum solution of mixing slowly pours on smooth surface, clean sheet glass, is coated onto with adjustable step instrument that is coated with On sheet glass, being then placed in baking oven, constant temperature 70 DEG C dries 2h；Finally take out sheet glass, scrape thin film with blade, obtain film, film Picture with reference to Fig. 1, wherein, in this film, by weight percentage, the composition of film includes: CsHSO447.37%；Mesoporous Al2O321.05%；Kynoar 31.58%.This film can be used as the PEM in fuel cell.
The mensuration of the proton conductivity of the film under embodiment 4 different temperatures
As in figure 2 it is shown, the S1 film prepared in embodiment 1, recording its film thickness is 100 μm, by electric impedance analyzer The proton conductivity recording 25 DEG C-100 DEG C can reach 10-4S·cm-1；At 100-200 DEG C, proton conductivity increases to 10-3S· cm-1, when 200 DEG C, its proton conductivity is up to 2.5 × 10-3S·cm-1。
The comparison of the resistance alcohol rate of the film of embodiment 5 present invention and Nafion membrane
Owing to DMFC (DMFC) can only use less than at a temperature of methanol boiling point, therefore, the present invention Determine the resistance alcohol rate of the film S2 prepared in embodiment 2 at a temperature of 25 DEG C-70 DEG C, as it is shown on figure 3, measurement result shows Under the temperature range of 25 DEG C-70 DEG C, the resistance alcohol rate of film is high 3 orders of magnitude than Nafion membrane, thus are particularly suited for direct methanol In fuel cell.
Above-described embodiment shows that the proton conductivity of the film that the present invention provides is 10 when 25 DEG C-100 DEG C-4S·cm-1；? When 100-200 DEG C, proton conductivity increases to 10-3S·cm-1, when 200 DEG C, its proton conductivity is up to 2.5 × 10-3S· cm-1.As can be seen here, the electrical conductivity of the film that the present invention provides is higher, is possible not only at low temperature (100 DEG C) used below, also simultaneously Can use under middle temperature (100-200 DEG C), Applicable temperature wider range.Additionally, due to the resistance alcohol rate of the film of present invention offer Higher, high 3 orders of magnitude than Nafion membrane, thus be particularly suited in DMFC.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention Within god and principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.

Claims (6)

1. a preparation method for film, comprises the following steps:
By CsHSO4With mesoporous Al2O3It is mixed to get mixture；
Described mixture is become mixed liquor with Kynoar solution mixing system；And
Use coating process that prepared by described mixed liquor film forming；
Wherein, the step of mixed liquor is become to farther include with described Kynoar solution mixing system in described mixture:
Kynoar is mixed with N,N-dimethylacetamide, is prepared as described Kynoar solution；And
Described mixture and described Kynoar solution are mixed to get described mixed liquor, and wherein, described mixture is with described The mass ratio of Kynoar is between 0.34 and 2.22；
Wherein, described by CsHSO4With mesoporous Al2O3The step being mixed to get mixture farther includes:
By described CsHSO4With described mesoporous Al2O3Mix and obtain mixture；
Described mixture is heated to 250 DEG C of also constant temperature 12 hours, is cooled to room temperature；And
Grind described mixture 5 minutes；
Wherein, described CsHSO4With described mesoporous Al2O3Mass ratio between 0.75 and 5.81；
Implement described Kynoar and described N,N-dimethylacetamide under 50 DEG C-70 DEG C heating and/or stirring condition The step of mixing, wherein, the time of described stirring is until forming the described Kynoar solution of clarification；
Under the conditions of stirring and/or supersonic oscillations, implement the step mixed by described mixture with described Kynoar solution Suddenly, wherein, the time of described stirring is 20-30 minute, and the time of described supersonic oscillations is 20-30 minute.
Preparation method the most according to claim 1, it is characterised in that described mixed liquor is prepared by described use coating process The step of film forming farther includes:
Utilize coating instrument to be coated on substrate by described mixed liquor, be dried described mixed liquor to generate described film；And
Described film is peeled off from described substrate.
Preparation method the most according to claim 2, it is characterised in that implement to be dried the step of described mixed liquor in an oven Suddenly, wherein, described dry temperature is 50 DEG C-70 DEG C, and the described dry time is 3-5 hour；
Described coating instrument is adjustable spreader, spin coater, automatic coating machine, coating machine；And
Described substrate is sheet glass.
Preparation method the most according to claim 1, it is characterised in that described film is PEM.
5. the film prepared according to the preparation method according to any one of claim 1-4, it is characterised in that with weight percent Than meter, the composition of described film includes:
CsHSO417.16%-47.37%
Mesoporous Al2O38.16%-22.84%；
Kynoar 31.58%-73.47%.
Film the most according to claim 5, it is characterised in that described film is PEM.
CN201310530700.7A 2013-10-30 2013-10-30 A kind of film and preparation method thereof Expired - Fee Related CN103554537B (en)

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CN105140545A (en) * 2015-08-04 2015-12-09 中国计量学院 Preparation technology of composite proton exchange membrane
CN105355937A (en) * 2015-12-08 2016-02-24 中国计量学院 Preparation process of membrane electrode assembly for proton exchange membrane fuel cell
CN107240705B (en) * 2017-05-10 2020-08-04 上海交通大学 Medium-temperature molten proton conductor electrolyte membrane and application
CN107331883B (en) * 2017-05-10 2020-07-14 上海交通大学 Intermediate-temperature proton exchange membrane and preparation method thereof
CN113410496B (en) * 2021-06-16 2023-02-14 东北大学秦皇岛分校 All-solid-state trace water-containing low-temperature applicable proton exchange membrane and preparation method thereof
CN113839074B (en) * 2021-09-24 2023-10-20 上海交通大学 Preparation method of solid acid proton conducting membrane

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