CN103811771B - A kind of method of modifying of the proton exchange membrane for direct methanol fuel cell - Google Patents

A kind of method of modifying of the proton exchange membrane for direct methanol fuel cell Download PDF

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CN103811771B
CN103811771B CN201410025449.3A CN201410025449A CN103811771B CN 103811771 B CN103811771 B CN 103811771B CN 201410025449 A CN201410025449 A CN 201410025449A CN 103811771 B CN103811771 B CN 103811771B
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solution
zeolite
proton exchange
type zeolite
exchange membrane
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CN103811771A (en
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武俊伟
崔彦辉
安德鲁·贝克
王洪波
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Shenzhen Graduate School Harbin Institute of Technology
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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/881—Electrolytic membranes
    • 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
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention discloses a kind of method of modifying of the proton exchange membrane for direct methanol fuel cell, it comprises the steps: to prepare nanoscale and submicron order Na-X zeolite with hydrothermal synthesis method; Be NH by the Na-X zeolite catalysts of preparation 4-X zeolite; By the NH of preparation 4-X zeolite adds in Nafion solution in proportion, reinvents legal system for composite membrane with solution.This composite membrane water absorbing properties, ion exchange capacity, proton conductive, methanol permeability are all better than unmodified Nafion film.Such as, compared to unmodified Nafion film, sub-micron NH 4it is many that the methanol permeability of-X/Nafion composite membrane have dropped half, and its selectivity has brought up to unadulterated 3 times.

Description

A kind of method of modifying of the proton exchange membrane for direct methanol fuel cell
Technical field
The present invention relates to the proton exchange membrane field of fuel cell, be specifically related to a kind of method of modifying of the proton exchange membrane for direct methanol fuel cell.
Background technology
Fuel cell is a class novel energy conversion equipment, has lot of advantages, and such as conversion efficiency is high, it is little to pollute and noise is little etc.Direct methanol fuel cell is fuel with methyl alcohol, is directly translated into electric energy, can be widely used in the various aspects of living, such as compact power, supply station, automobile etc.Wherein, proton exchange membrane is the core component of direct methanol fuel cell, at present the main Nafion(Perfluorinated ion exchanger resin using du pont company to produce) film.But Nafion film has some shortcomings when being applied to direct methanol fuel cell, such as there is higher methanol permeability and under low humidity hot conditions proton conductivity not high.Therefore, carry out modification to Nafion film to be necessary very much.
Wherein organic or inorganic compound Nafion film due to technique simple, result and pure Nafion film contrast obviously, and receive the concern of most researcher.Introducing silicon dioxide, aerosil, basic zirconium phosphate, organic modified silicate, phosphotungstic acid, silylation filler, phosphomolybdic acid, zeolite etc. is conventional means.Usually the method preparing compound proton exchange membrane has two kinds: one is in-situ sol-gel; Another kind is that method reinvented by mixed liquor.In-situ sol-gel be Nafion film is immersed in containing to be used for modification inorganic particle solution in, such inorganic particle will grow in Nafion bunch.But, method reinvented by mixed liquor is will be used for the inorganic particle of modification Nafion to join in the mixed liquor of Nafion and solvent, fully mixes, then is transferred to by mixed liquor in specific mould, solvent evaporated at a certain temperature, just obtains the method for composite membrane.Solution reinvents method because its technique is simple, be easy to operation, film forming is evenly adopted by the present invention, but the present invention is equally applicable to composite membrane prepared by original position membrane formation process.
Summary of the invention
Object of the present invention is exactly based on above-mentioned starting point, a kind of method of modifying of the proton exchange membrane for direct methanol fuel cell is provided, its method of modifying is simple and reliable, workable, the property indices of modified proton exchange membrane all increases, especially its methanol permeability improves more, and its selectivity has brought up to original 3 times.
The invention provides a kind of method of modifying of the proton exchange membrane for direct methanol fuel cell, its concrete grammar is as follows:
Step one: utilization hydrothermal synthesis method preparation size is the submicron order Na-X type zeolite of 100 ~ 500nm; Sodium metasilicate (Na 2siO 39H 2and aluminium hydroxide (Al (OH) O) 3) respectively as silicon source and the aluminium source of preparing submicron order Na-X type zeolite; Silicon-aluminum sol is by the sodium aluminate solution of fresh preparation and sodium silicate solution routine NaAlO in molar ratio 2: (3 ~ 5) SiO 2: (15 ~ 17) NaOH:(300 ~ 350) H 2o synthesizes preparation rapidly;
Or utilization hydrothermal synthesis method preparation size is the nanoscale Na-X type zeolite of 10 ~ 100nm; The preparation tetraethoxysilane of nanoscale Na-X type zeolite is as silicon source; Silicon-aluminum sol is by the sodium aluminate solution of fresh preparation and teos solution example (4.5 ~ 7) Na in molar ratio 2o:1.0Al 2o 3: (3 ~ 5) SiO 2: (180 ~ 200) H 2prepared by O;
Step 2: preparation NH 4-X-type zeolite; After preparing Na-X type zeolite, and then it is transformed, replace the sodium ion in Na-X type zeolite completely with ammonium ion, obtain NH 4-X-type zeolite;
Step 3: prepare compound proton exchange membrane; By the NH prepared 4-X-type zeolite uses solution to reinvent legal system for compound proton exchange membrane.
As a further improvement on the present invention, in step one, the concrete synthetic method of submicron order Na-X type zeolite is as follows:
Adding aluminium hydroxide by the sodium hydroxide solution prepared, 90 ~ 100 DEG C of stirred in water bath to dissolving, being cooled to room temperature stand-by;
Again this solution is mixed with deionized water and NaOH, and stir 0.5 ~ 1.5 hour in ice-water bath;
Then with Na 2siO 3solution mixes rapidly, and ice-water bath stirs 0.9 ~ 1.1 hour;
Then solution is transferred in Teflon liner cup, then liner cup is put into stainless steel cauldron, afterwards hydrothermal crystallization 7.5 ~ 8.5 hours in the hot case of 95 ~ 105 DEG C;
Finally, the zeolite of advantages of good crystallization is taken out, filter, wash to pH value≤10, dried for standby.
As a further improvement on the present invention, in step one, nanoscale Na-X type zeolite synthesis concrete steps are as follows:
The sodium aluminate solution prepared is transferred in beaker, and stirs 0.5 ~ 1.5 hour in ice-water bath;
Then 2 ~ 2.2 times of tetraethoxysilanes to the ice-water bath process of sodium metaaluminate mole are slowly added drop-wise in sodium aluminate solution, and stir 5.5 ~ 6.5 hours in ice-water bath, proceed to stirred at ambient temperature afterwards 20 ~ 30 hours;
Then the solution be stirred is proceeded in Teflon liner cup, liner cup is put into stainless steel cauldron, then reactor is put into the hot case crystallization 2 ~ 4 days of 50 ~ 65 DEG C;
Finally, taken out by zeolite good for hydrothermal crystallization, centrifugation, washs to pH value≤10, dried for standby.
As a further improvement on the present invention, step 2 is specific as follows:
First the Na-X type zeolite of 0.5 ~ 5.0g is put into the ammonium salt solution that 80 ~ 160ml is not less than 1mol/L, stir ultrasonic process 5 ~ 15 minutes;
Again the solution handled well is proceeded in the stainless steel cauldron of Teflon liner cup, place 20 ~ 30 hours in the hot case of 50 ~ 70 DEG C;
Then the solution reacted is taken out, be cooled to room temperature, centrifuge washing 4 ~ 6 times;
Again the zeolite that centrifuge washing is good is put into the ammonium salt solution being not less than 1mol/L, stir ultrasonic process;
Then the solution handled well is proceeded in the stainless steel cauldron of Teflon liner cup, place in the hot case of 50 ~ 70 DEG C;
Repeat above-mentioned steps again 1 ~ 2 time, finally, the zeolite that processes is taken out centrifugal, washing 4 ~ 6 times, dried for standby.
As a further improvement on the present invention, ammonium salt solution is ammonium chloride.
As a further improvement on the present invention, step 3 is specific as follows:
First the zeolite of the 3wt% ~ 8wt% of composite membrane quality and 1.5 ~ 2.5 times of DMF mix and blends to proton exchange coating solution, ultrasonic wave process, until mix;
Again by mixed liquor and 15 ~ 25ml proton exchange coating solution mix and blend, ultrasonic process
Again the mixed liquor handled well is transferred in Teflon mould, build with the uniform grinding tool lid of porous, prevent solvent from evaporating too fast and causing composite membrane uneven;
The mould installing solution is placed on totally, in the air dry oven of level, be evaporated at 60 ~ 90 DEG C without solution;
Then the mould being evaporated solvent is placed in the drying box of 140 ~ 170 DEG C, film is aging; Finally, etc. mold cools down to room temperature, add deionized water, after immersion, film is taken out, dried for standby.
As a further improvement on the present invention, the bottom of Teflon mould is level.
The invention has the beneficial effects as follows:
Use inorganic material NH 4-X-type zeolite mixes mutually with proton exchange membrane original solution, reinvents legal system for proton exchange membrane by solution.NH 4the cross section of the proton exchange membrane of different content prepared by-X-type zeolite is all relatively more even, and the associativity of zeolite and proton exchange membrane is good.The water absorbing properties of modified composite membrane, ion exchange capacity, proton conductive and methanol permeability all make moderate progress, and especially its methanol permeability improves more.Such as, compared to unmodified Nafion film, sub-micron NH 4it is many that the methanol permeability of-X/Nafion composite membrane have dropped half, and its selectivity has brought up to unadulterated 3 times.
Notable feature of the present invention is in preparation process two, repeatedly soaks Na-X type zeolite prepare NH with ammonium salt solution 4-X-type zeolite, and in preparation process three, added in proton exchange coating solution, prepare compound proton exchange membrane.Modified composite membrane water absorbing properties, ion exchange capacity, proton conductive, methanol permeability are all better than unmodified proton exchange membrane.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for modifying of a kind of proton exchange membrane for direct methanol fuel cell of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention will be further described.
Embodiment 1
A kind of method of modifying of the proton exchange membrane for direct methanol fuel cell
1. use hydrothermal synthesis method preparation size to be 10 ~ 100nm nano level Na-X type zeolite.The preparation tetraethoxysilane of nanoscale Na-X type zeolite is as silicon source, and silicon-aluminum sol is by the sodium aluminate solution of fresh preparation and teos solution routine 5.5Na in molar ratio 2o:1.0Al 2o 3: 4.0SiO 2: 190H 2prepared by O.6.8gNaOH and 9gH 2o mixed dissolution, adds 3.5gAl (OH) 3stirring and dissolving at 100 DEG C, is cooled to room temperature, then with 40gH 2o mixes.The sodium aluminate solution prepared is transferred in beaker, and stirs 1 hour in ice-water bath.Then 2 times of tetraethoxysilanes to the ice-water bath process of sodium metaaluminate mole are slowly added drop-wise in sodium aluminate solution, and stir 6 hours in ice-water bath, proceed to stirred at ambient temperature afterwards 24 hours.Then the solution be stirred is proceeded in Teflon liner cup, liner cup is put into stainless steel cauldron, then reactor is put into the hot case crystallization 2 days of 60 DEG C.Finally, taken out by zeolite good for hydrothermal crystallization, centrifugation, washs to pH value≤10, dried for standby.
2., after preparing nanoscale Na-X type zeolite, and then conversion is carried out to it and obtain nanoscale NH 4-X-type zeolite.First the nanoscale Na-X type zeolite of 3g is put into the ammonium chloride solution of 160ml1mol/L, stir ultrasonic process 30min.Again the solution handled well is proceeded in the stainless steel cauldron of Teflon liner cup, in the hot case of 60 DEG C, place 20h.Then the solution reacted is taken out, be cooled to room temperature, centrifuge washing five times.Again the zeolite that centrifuge washing is good is put into the ammonium chloride solution identical with first step concentration, stir ultrasonic process 30min.Then the solution handled well is proceeded in the stainless steel cauldron of Teflon liner cup, in the hot case of 60 DEG C, place 20h.Repeat above-mentioned steps more once.Finally, the zeolite that processes is taken out centrifugal, washing five times, in 60 DEG C of drying boxes dry 24 hours.
3. the nanoscale NH will prepared 4-X-type zeolite uses solution to reinvent legal system for compound proton exchange membrane.Concrete preparation process is as follows: first the NH of 0.05g 4-X-type zeolite and the DMF mix and blend, the ultrasonic wave process that double proton exchange coating solution, until mix.Again by mixed liquor and 20ml proton exchange coating solution mix and blend, ultrasonic process.Again the mixed liquor handled well is transferred in the Teflon mould of 70mm × 70mm × 30mm, build with the uniform grinding tool lid of porous, prevent solvent from evaporating too fast and causing composite membrane uneven.In addition, the level of mold bottom must be ensured.The mould installing solution is placed in clean air dry oven, is evaporated to without solution at 80 DEG C.Then the mould being evaporated solvent is placed in the drying box of 160 DEG C, film is aging.Finally, etc. mold cools down to room temperature, add deionized water, after immersion, film is carefully taken out.
5wt% nanoscale NH prepared by the present invention 4-X/Nafion compound proton exchange membrane has good combination property, and wherein, water absorption is 23%, and ion exchange capacity is 0.951meq/gr, and methanol permeability is 3.2cm 2/ s, proton conductivity is 141.8mS/cm, and selectivity is 39.6S*s/cm 3.
Embodiment 2
A kind of method of modifying of the proton exchange membrane for direct methanol fuel cell
1. utilization hydrothermal synthesis method preparation size is the submicron order Na-X zeolite of 100 ~ 500nm.Sodium metasilicate (Na 2siO 39H 2and aluminium hydroxide (Al (OH) O) 3) respectively as silicon source and the aluminium source of preparing submicron order Na-X type zeolite.Silicon-aluminum sol is by the sodium aluminate solution of fresh preparation and sodium silicate solution routine NaAlO in molar ratio 2: 4SiO 2: 16NaOH:325H 2o synthesizes preparation rapidly.Concrete synthesis step is as follows:
First, adding 4.9g aluminium hydroxide in the sodium hydroxide solution of the mass ratio 1:1 prepared by 10g, 90 ~ 100 DEG C of stirred in water bath to dissolving, being cooled to room temperature stand-by.Again this solution is mixed with 10g deionized water and NaOH.Get the solution that 5g mixes to mix with 30.6g deionized water and 2.9g NaOH, and stir 1 hour in ice-water bath.Then with Na 2siO 3solution (Na 2siO 314.3g, H 2o30.4g) mix rapidly, and ice-water bath stirs 1 hour.Then solution is transferred in Teflon liner cup, then liner cup is put into stainless steel cauldron, afterwards hydrothermal crystallization 8 hours in the hot case of 98 DEG C.Finally, the zeolite of advantages of good crystallization is taken out, filter, wash to pH value≤10, dried for standby.
2., after preparing submicron order Na-X type zeolite, and then conversion is carried out to it and obtain submicron order NH 4-X-type zeolite.First the Na-X type zeolite of 3g is put into the ammonium chloride solution of 160ml1mol/L, stir ultrasonic process 30min.Again the solution handled well is proceeded in the stainless steel cauldron of Teflon liner cup, in the hot case of 60 DEG C, place 20h.Then the solution reacted is taken out, be cooled to room temperature, centrifuge washing five times.Again the zeolite that centrifuge washing is good is put into the ammonium chloride solution identical with first step concentration, stir ultrasonic process 30min.Then the solution handled well is proceeded in the stainless steel cauldron of Teflon liner cup, in the hot case of 60 DEG C, place 20h.Repeat above-mentioned steps more once.Finally, the zeolite that processes is taken out centrifugal, washing five times, in 60 DEG C of drying boxes dry 24 hours.
3. the submicron order NH will prepared 4-X-type zeolite uses solution to reinvent legal system for compound proton exchange membrane.In order to make doping evenly, first the zeolite of preparation is pressed 0.05g and 40mlDMF mix and blend 30 minutes, then ultrasonic wave process 30 minutes.Again by mixed liquor and 20mlNafion solution mix and blend 30 minutes, more ultrasonic process 30 minutes.The mixed liquor handled well is transferred in the Teflon mould of 70mm × 70mm × 30mm, build with the uniform grinding tool lid of porous, prevent solvent from evaporating too fast and causing composite membrane uneven.In addition, the level of mold bottom must be ensured.The mould installing solution is placed in clean air dry oven, at 80 DEG C, evaporates about 20 hours.The mould being evaporated solvent is placed in the drying box of 160 DEG C, by aging for film 1 hour.Afterwards etc. mold cools down is to room temperature, adds deionized water, soaks film 30 minutes, is carefully taken out by film.
5wt% sub-micron NH prepared by the present invention 4-X/Nafion compound proton exchange membrane has good combination property, and wherein, water absorption is 21%, and ion exchange capacity is 0.937meq/gr, and methanol permeability is 2.28cm 2/ s, proton conductivity is 134.9mS/cm, and selectivity is 59.2S*s/cm 3.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.

Claims (4)

1., for a method of modifying for the proton exchange membrane of direct methanol fuel cell, it is characterized in that:
Step one: utilization hydrothermal synthesis method preparation size is the submicron order Na-X type zeolite of 100 ~ 500nm; Sodium metasilicate (Na 2siO 3) and aluminium hydroxide (Al (OH) 3) respectively as silicon source and the aluminium source of preparing submicron order Na-X type zeolite; Your ratio NaAlO of the sodium aluminate solution of fresh preparation, sodium silicate solution, NaOH and hydromassage 2: (3 ~ 5) Na 2siO 3: (5 ~ 11) NaOH:(300 ~ 350) H 2o is mixed with rapidly sub-micron Na-X zeolite: add aluminium hydroxide by the sodium hydroxide solution prepared, and 90 ~ 100 DEG C of stirred in water bath to dissolving, is cooled to room temperature stand-by; Again this solution is mixed with deionized water and NaOH, and stir 0.5 ~ 1.5 hour in ice-water bath; Then with Na 2siO 3solution mixes rapidly, and ice-water bath stirs 0.9 ~ 1.1 hour, can obtain silicon-aluminum sol; Then silicon-aluminum sol is transferred in Teflon liner cup, then liner cup is put into stainless steel cauldron, afterwards hydrothermal crystallization 7.5 ~ 8.5 hours in the hot case of 95 ~ 105 DEG C; Finally, taken out by the zeolite of advantages of good crystallization, filter, wash to pH value≤10, drying can obtain sub-micron Na-X type zeolite;
Or utilization hydrothermal synthesis method preparation size is the nanoscale Na-X type zeolite of 10 ~ 100nm; The preparation tetraethoxysilane of nanoscale Na-X type zeolite is as silicon source; Your ratio (7 ~ 12) NaOH:2NaAlO of the sodium aluminate solution of fresh preparation, teos solution, NaOH and hydromassage 2: (3 ~ 5) Si (OC 2h 5) 4: (180 ~ 200) H 2o is mixed with nanometer Na-X zeolite: be transferred in beaker by the sodium aluminate solution prepared, and stirs 0.5 ~ 1.5 hour in ice-water bath; Then 2 ~ 2.2 times of tetraethoxysilanes to the ice-water bath process of sodium metaaluminate mole are slowly added drop-wise in sodium aluminate solution, and stir 5.5 ~ 6.5 hours in ice-water bath, proceed to stirred at ambient temperature afterwards 20 ~ 30 hours; Then the solution be stirred is proceeded in Teflon liner cup, liner cup is put into stainless steel cauldron, then reactor is put into the hot case crystallization 2 ~ 4 days of 50 ~ 65 DEG C; Finally, taken out by zeolite good for hydrothermal crystallization, centrifugation, washs to pH value≤10, dried for standby;
Step 2: preparation NH 4-X-type zeolite; After preparing Na-X type zeolite, and then it is transformed, replace the sodium ion in Na-X type zeolite completely with ammonium ion, obtain NH 4-X-type zeolite,
Its concrete steps are as follows:
First the Na-X type zeolite of 0.5 ~ 5.0g is put into the ammonium salt solution that 80 ~ 160ml is not less than 1mol/L, stir ultrasonic process 5 ~ 15 minutes;
Again the solution handled well is proceeded in the stainless steel cauldron of Teflon liner cup, place 20 ~ 30 hours in the hot case of 50 ~ 70 DEG C;
Then the solution reacted is taken out, be cooled to room temperature, centrifuge washing 4 ~ 6 times;
Again the zeolite that centrifuge washing is good is put into the ammonium chloride solution being not less than 1mol/L, stir ultrasonic process;
Then the solution handled well is proceeded in the stainless steel cauldron of Teflon liner cup, place in the hot case of 50 ~ 70 DEG C;
Repeat above-mentioned steps again 1 ~ 2 time, finally, the zeolite that processes is taken out centrifugal, washing 4 ~ 6 times, dried for standby;
Step 3: prepare compound proton exchange membrane; By the NH prepared 4-X-type zeolite uses solution to reinvent legal system for compound proton exchange membrane.
2. the method for modifying of a kind of proton exchange membrane for direct methanol fuel cell according to claim 1, is characterized in that: in step 2, and ammonium salt solution is ammonium chloride.
3. the method for modifying of a kind of proton exchange membrane for direct methanol fuel cell according to claim 1, is characterized in that: step 3 is specific as follows:
First the zeolite of the 3wt% ~ 8wt% of composite membrane quality and 1.5 ~ 2.5 times of DMF mix and blends to proton exchange coating solution, ultrasonic wave process, until mix;
Again by mixed liquor and 15 ~ 25ml proton exchange coating solution mix and blend, ultrasonic process;
Again the mixed liquor handled well is transferred in Teflon mould, build with the uniform grinding tool lid of porous, prevent solvent from evaporating too fast and causing composite membrane uneven;
The mould installing solution is placed in clean air dry oven, is evaporated at 60 ~ 90 DEG C without solution;
Then the mould being evaporated solvent is placed in the drying box of 140 ~ 170 DEG C, film is aging; Finally, etc. mold cools down to room temperature, add deionized water, after immersion, film is taken out, dried for standby.
4. the method for modifying of a kind of proton exchange membrane for direct methanol fuel cell according to claim 3, is characterized in that: the bottom of Teflon mould is level.
CN201410025449.3A 2014-01-20 2014-01-20 A kind of method of modifying of the proton exchange membrane for direct methanol fuel cell Expired - Fee Related CN103811771B (en)

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CN106356548B (en) * 2016-11-28 2019-05-10 哈尔滨工业大学深圳研究生院 A kind of method of modifying of the proton exchange membrane for direct methanol fuel cell
CN106784917B (en) * 2016-12-16 2019-03-19 哈尔滨工业大学深圳研究生院 A kind of method of modifying of the proton exchange membrane for all-vanadium flow battery
CN108134116B (en) * 2017-12-26 2020-03-20 成都新柯力化工科技有限公司 Poly furfuryl alcohol modified fuel cell proton exchange membrane and modification method thereof

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