CN103811771A - Modification method for proton exchange membrane of direct-methanol fuel cell - Google Patents

Modification method for proton exchange membrane of direct-methanol fuel cell Download PDF

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CN103811771A
CN103811771A CN201410025449.3A CN201410025449A CN103811771A CN 103811771 A CN103811771 A CN 103811771A CN 201410025449 A CN201410025449 A CN 201410025449A CN 103811771 A CN103811771 A CN 103811771A
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solution
proton exchange
zeolite
type zeolite
exchange membrane
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CN103811771B (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 modification method for a proton exchange membrane of a direct-methanol fuel cell. The modification method for the proton exchange membrane of the direct-methanol fuel cell comprises the following steps: preparing nanoscale and submicron order Na-X zeolite; converting the prepared Na-X zeolite into NH4-X zeolite; adding the prepared NH4-X zeolite into a Nafion solution in proportion, and preparing a composite membrane by a solution remodeling method. The water absorption performance, the ion exchange capacity, the proton conductivity and the methyl alcohol permeability of the composite membrane are all superior to those of the unmodified Nafion membrane, for example, compared with the unmodified Nafion membrane, the methyl alcohol permeability of the submicron NH4-X/Nafion composite membrane is reduced by more than a half, and the selectivity is improved to 3 times of that of the undoped membrane.

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, such as conversion efficiency is high, it is little to pollute and noise is little etc.Direct methanol fuel cell, take methyl alcohol as fuel, is directly translated into electric energy, can be widely used in the various aspects of life, 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(perfluorinate ion exchange resin that uses du pont company to produce) film.But Nafion film has some shortcomings while being applied to direct methanol fuel cell, for example there is higher methanol permeability and under low humidity hot conditions proton conductivity not high.Therefore, Nafion film is carried out to modification is necessary very much.
Wherein the compound Nafion film of organic or inorganic is because technique is simple, and result and the contrast of pure Nafion film are obvious, and has received most researchers' concern.Introducing silicon dioxide, aerosil, basic zirconium phosphate, organic modified silicate, phosphotungstic acid, silylation filler, phosphomolybdic acid, zeolite etc. is conventional means.Conventionally the method for preparing compound proton exchange membrane has two kinds: one is in-situ sol-gel; Another kind is that mixed liquor is reinvented method.In-situ sol-gel is Nafion film to be immersed in to contain will be used in the solution of inorganic particle of modification, and inorganic particle will be grown in Nafion bunch like this.But, it is will be used for the inorganic particle of modification Nafion to join in the mixed liquor of Nafion and solvent that mixed liquor is reinvented method, fully mixes, then mixed liquor is transferred in specific mould, solvent evaporated at a certain temperature, just obtains the method for composite membrane.Solution reinvent method because its technique is simple, easy operating, film forming evenly adopt by the present invention, still, the present invention is equally applicable to the standby composite membrane of original position film forming legal system.
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 the proton exchange membrane after modification all increases, especially its methanol permeability improvement is more, and its selectivity has been brought up to original 3 times.
The method of modifying that the invention provides a kind of proton exchange membrane for direct methanol fuel cell, its concrete grammar is as follows:
Step 1: use the submicron order Na-X type zeolite that hydrothermal synthesis method preparation size is 100～500nm; Sodium metasilicate (Na 2siO 39H 2and aluminium hydroxide (Al (OH) O) 3) respectively as the He Lv source, silicon source of preparing submicron order Na-X type zeolite; Silicon-aluminum sol is by sodium aluminate solution and the sodium silicate solution routine NaAlO in molar ratio of fresh preparation 2: (3～5) SiO 2: (15～17) NaOH:(300～350) H 2o is synthetic preparation rapidly;
Or use the nanoscale Na-X type zeolite that hydrothermal synthesis method preparation size is 10～100nm; The preparation of nanoscale Na-X type zeolite uses tetraethoxysilane as silicon source; Silicon-aluminum sol is by sodium aluminate solution and teos solution example (4.5～7) Na in molar ratio of fresh preparation 2o:1.0Al 2o 3: (3～5) SiO 2: (180～200) H 2o preparation;
Step 2: preparation NH 4-X-type zeolite; Prepare after 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 preparing 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 1, the concrete synthetic method of submicron order Na-X type zeolite is as follows:
To in the sodium hydroxide solution preparing, add aluminium hydroxide, to dissolving, be cooled to room temperature stand-by 90～100 ℃ of stirred in water bath;
Again this solution is mixed with deionized water and NaOH, and in ice-water bath, stir 0.5～1.5 hour;
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 ℃;
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 1, the synthetic concrete steps of nanoscale Na-X type zeolite are as follows:
The sodium aluminate solution preparing is transferred in beaker, and in ice-water bath, stirs 0.5～1.5 hour;
Then 2～2.2 times of tetraethoxysilanes to the ice-water bath processing of sodium metaaluminate mole are slowly added drop-wise in sodium aluminate solution, and in ice-water bath, stir 5.5～6.5 hours, proceed to afterwards under room temperature and stir 20～30 hours;
Then the solution being 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 ℃;
Finally, zeolite good hydrothermal crystallization is taken out, centrifugation, washs to pH value≤10, dried for standby.
As a further improvement on the present invention, step 2 is specific as follows:
The ammonium salt solution of first the Na-X type zeolite of 0.5～5.0g being put into 80～160ml and be not less than 1mol/L, stirs ultrasonic processing 5～15 minutes;
Again the solution of handling well is proceeded in the stainless steel cauldron of Teflon liner cup, in the hot case of 50～70 ℃, place 20～30 hours;
Then the solution having reacted is taken out, be cooled to room temperature, centrifuge washing 4～6 times;
Again the good zeolite of centrifuge washing is put into the ammonium salt solution that is not less than 1mol/L, stir ultrasonic processing;
Then the solution of handling well is proceeded in the stainless steel cauldron of Teflon liner cup, in the hot case of 50～70 ℃, place;
Repeat again above-mentioned steps 1～2 time, last, the zeolite of handling is taken out to 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 to the DMF of proton exchange coating solution mix and blend, ultrasonic wave processing, until mix;
Again by mixed liquor and 15～25ml proton exchange coating solution mix and blend, ultrasonic processing
Again the mixed liquor of handling well is transferred in Teflon mould, built with the uniform grinding tool lid of porous, prevent that solvent from evaporating too fast and causing composite membrane inhomogeneous;
The mould that installs solution is placed on totally, in the air dry oven of level, at 60～90 ℃, is evaporated to without solution;
Then the mould that evaporates solvent is placed in the drying box of 140～170 ℃, film is aging; Finally, to room temperature, add deionized water etc. mold cools down, after immersion, film is taken out to 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 more even, and the associativity of zeolite and proton exchange membrane is good.Water absorbing properties, ion exchange capacity, proton conductive and the methanol permeability of the composite membrane after modification all make moderate progress, and especially its methanol permeability improves more.For example,, than unmodified Nafion film, sub-micron NH 4the methanol permeability of-X/Nafion composite membrane the half that declined is many, and its selectivity has been 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.Composite membrane water absorbing properties after modification, 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. using hydrothermal synthesis method preparation size is the nano level Na-X type of 10～100nm zeolite.The preparation of nanoscale Na-X type zeolite is with tetraethoxysilane as silicon source, and silicon-aluminum sol is by sodium aluminate solution and the teos solution routine 5.5Na in molar ratio of fresh preparation 2o:1.0Al 2o 3: 4.0SiO 2: 190H 2o preparation.6.8g NaOH and 9g H 2o mixed dissolution, adds 3.5g Al (OH) 3stirring and dissolving at 100 ℃, is cooled to room temperature, then with 40g H 2o mixes.The sodium aluminate solution preparing is transferred in beaker, and in ice-water bath, stirs 1 hour.Then 2 times of tetraethoxysilanes to the ice-water bath processing of sodium metaaluminate mole are slowly added drop-wise in sodium aluminate solution, and in ice-water bath, stir 6 hours, proceed to afterwards under room temperature and stir 24 hours.Then the solution being 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 ℃.Finally, zeolite good hydrothermal crystallization is taken out, centrifugation, washs to pH value≤10, dried for standby.
2. prepare after nanoscale Na-X type zeolite, and then it is transformed and obtains nanoscale NH 4-X-type zeolite.The ammonium chloride solution of first the nanoscale Na-X type zeolite of 3g being put into 160ml1mol/L, stirs ultrasonic processing 30min.Again the solution of handling well is proceeded in the stainless steel cauldron of Teflon liner cup, in the hot case of 60 ℃, place 20h.Then the solution having reacted is taken out, be cooled to room temperature, centrifuge washing five times.Again the good zeolite of centrifuge washing is put into the ammonium chloride solution identical with first step concentration, stir ultrasonic processing 30min.Then the solution of handling well is proceeded in the stainless steel cauldron of Teflon liner cup, in the hot case of 60 ℃, place 20h.Repeat again above-mentioned steps once.Finally, the zeolite handled is taken out to centrifugal, washing five times, in 60 ℃ of drying boxes dry 24 hours.
3. by the nanoscale NH preparing 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 processing that double proton exchange coating solution, until mix.Again by mixed liquor and 20ml proton exchange coating solution mix and blend, ultrasonic processing.Again the mixed liquor of handling well is transferred in the Teflon mould of 70mm × 70mm × 30mm, built with the uniform grinding tool lid of porous, prevent that solvent from evaporating too fast and causing composite membrane inhomogeneous.In addition, must guarantee the level of mold bottom.The mould that installs solution is placed in clean air dry oven, at 80 ℃, is evaporated to without solution.Then the mould that evaporates solvent is placed in the drying box of 160 ℃, film is aging.Finally, to room temperature, add deionized water etc. mold cools down, 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, 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. use the submicron order Na-X zeolite that hydrothermal synthesis method preparation size is 100～500nm.Sodium metasilicate (Na 2siO 39H 2and aluminium hydroxide (Al (OH) O) 3) respectively as the He Lv source, silicon source of preparing submicron order Na-X type zeolite.Silicon-aluminum sol is by sodium aluminate solution and the sodium silicate solution routine NaAlO in molar ratio of fresh preparation 2: 4SiO 2: 16NaOH:325H 2o is synthetic preparation rapidly.Concrete synthesis step is as follows:
First, in the sodium hydroxide solution of the mass ratio 1:1 that 10g is prepared, add 4.9g aluminium hydroxide, to dissolving, be cooled to room temperature stand-by 90～100 ℃ of stirred in water bath.Again this solution is mixed with 10g deionized water and NaOH.Get the solution that 5g mixes and mix with 30.6g deionized water and 2.9g NaOH, and in ice-water bath, stir 1 hour.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 ℃.Finally, the zeolite of advantages of good crystallization is taken out, filter, wash to pH value≤10, dried for standby.
2. prepare after submicron order Na-X type zeolite, and then it is transformed and obtains 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, stirred ultrasonic processing 30min.Again the solution of handling well is proceeded in the stainless steel cauldron of Teflon liner cup, in the hot case of 60 ℃, place 20h.Then the solution having reacted is taken out, be cooled to room temperature, centrifuge washing five times.Again the good zeolite of centrifuge washing is put into the ammonium chloride solution identical with first step concentration, stir ultrasonic processing 30min.Then the solution of handling well is proceeded in the stainless steel cauldron of Teflon liner cup, in the hot case of 60 ℃, place 20h.Repeat again above-mentioned steps once.Finally, the zeolite handled is taken out to centrifugal, washing five times, in 60 ℃ of drying boxes dry 24 hours.
3. by the submicron order NH preparing 4-X-type zeolite uses solution to reinvent legal system for compound proton exchange membrane.In order to make doping more even, first the zeolite of preparation press to 0.05g and 40ml DMF mix and blend 30 minutes, then ultrasonic wave processing 30 minutes.Again by mixed liquor and 20ml Nafion solution mix and blend 30 minutes, more ultrasonic processing 30 minutes.The mixed liquor of handling well is transferred in the Teflon mould of 70mm × 70mm × 30mm, built with the uniform grinding tool lid of porous, prevent that solvent from evaporating too fast and causing composite membrane inhomogeneous.In addition, must guarantee the level of mold bottom.The mould that installs solution is placed in clean air dry oven, at 80 ℃, evaporates about 20 hours.The mould that evaporates solvent is placed in the drying box of 160 ℃, by aging film 1 hour.Afterwards etc. mold cools down, to room temperature, adds deionized water, soaks film 30 minutes, and film is carefully taken out.
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, 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, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.

Claims (7)

1. for a method of modifying for the proton exchange membrane of direct methanol fuel cell, it is characterized in that:
Step 1: use the submicron order Na-X type zeolite that hydrothermal synthesis method preparation size is 100～500nm; Sodium metasilicate (Na 2siO 39H 2and aluminium hydroxide (Al (OH) O) 3) respectively as the He Lv source, silicon source of preparing submicron order Na-X type zeolite; Silicon-aluminum sol is by sodium aluminate solution and the sodium silicate solution routine NaAlO in molar ratio of fresh preparation 2: (3～5) SiO 2: (15～17) NaOH:(300～350) H 2o is synthetic preparation rapidly;
Or use the nanoscale Na-X type zeolite that hydrothermal synthesis method preparation size is 10～100nm; The preparation of nanoscale Na-X type zeolite uses tetraethoxysilane as silicon source; Silicon-aluminum sol is by sodium aluminate solution and teos solution example (4.5～7) Na in molar ratio of fresh preparation 2o:1.0Al 2o 3: (3～5) SiO 2: (180～200) H 2o preparation;
Step 2: preparation NH 4-X-type zeolite; Prepare after 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 preparing 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 1, the concrete synthetic method of submicron order Na-X type zeolite is as follows:
To in the sodium hydroxide solution preparing, add aluminium hydroxide, to dissolving, be cooled to room temperature stand-by 90～100 ℃ of stirred in water bath;
Again this solution is mixed with deionized water and NaOH, and in ice-water bath, stir 0.5～1.5 hour;
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 ℃;
Finally, the zeolite of advantages of good crystallization is taken out, filter, wash to pH value≤10, dried for standby.
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: in step 1, the synthetic concrete steps of nanoscale Na-X type zeolite are as follows:
The sodium aluminate solution preparing is transferred in beaker, and in ice-water bath, stirs 0.5～1.5 hour;
Then 2～2.2 times of tetraethoxysilanes to the ice-water bath processing of sodium metaaluminate mole are slowly added drop-wise in sodium aluminate solution, and in ice-water bath, stir 5.5～6.5 hours, proceed to afterwards under room temperature and stir 20～30 hours;
Then the solution being 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 ℃;
Finally, zeolite good hydrothermal crystallization is taken out, centrifugation, washs to pH value≤10, dried for standby.
4. 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 2 is specific as follows:
The ammonium salt solution of first the Na-X type zeolite of 0.5～5.0g being put into 80～160ml and be not less than 1mol/L, stirs ultrasonic processing 5～15 minutes;
Again the solution of handling well is proceeded in the stainless steel cauldron of Teflon liner cup, in the hot case of 50～70 ℃, place 20～30 hours;
Then the solution having reacted is taken out, be cooled to room temperature, centrifuge washing 4～6 times;
Again the good zeolite of centrifuge washing is put into the ammonium chloride solution that is not less than 1mol/L, stir ultrasonic processing;
Then the solution of handling well is proceeded in the stainless steel cauldron of Teflon liner cup, in the hot case of 50～70 ℃, place;
Repeat again above-mentioned steps 1～2 time, last, the zeolite of handling is taken out to centrifugal, washing 4～6 times, dried for standby.
5. the method for modifying of a kind of proton exchange membrane for direct methanol fuel cell according to claim 4, is characterized in that: ammonium salt solution is ammonium chloride.
6. 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 to the DMF of proton exchange coating solution mix and blend, ultrasonic wave processing, until mix;
Again by mixed liquor and 15～25ml proton exchange coating solution mix and blend, ultrasonic processing;
Again the mixed liquor of handling well is transferred in Teflon mould, built with the uniform grinding tool lid of porous, prevent that solvent from evaporating too fast and causing composite membrane inhomogeneous;
The mould that installs solution is placed in clean air dry oven, at 60～90 ℃, is evaporated to without solution;
Then the mould that evaporates solvent is placed in the drying box of 140～170 ℃, film is aging; Finally, to room temperature, add deionized water etc. mold cools down, after immersion, film is taken out to dried for standby.
7. changing of a kind of proton exchange membrane for direct methanol fuel cell according to claim 6
Property method, 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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CN106784917A (en) * 2016-12-16 2017-05-31 哈尔滨工业大学深圳研究生院 A kind of method of modifying of the PEM for all-vanadium flow battery
CN108134116A (en) * 2017-12-26 2018-06-08 成都新柯力化工科技有限公司 A kind of poly- furfuryl alcohol modification fuel battery proton exchange film and its method of modifying

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CN106356548A (en) * 2016-11-28 2017-01-25 哈尔滨工业大学深圳研究生院 Modification method for proton exchange membrane of direct methanol fuel cell
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
CN106784917A (en) * 2016-12-16 2017-05-31 哈尔滨工业大学深圳研究生院 A kind of method of modifying of the PEM for all-vanadium flow battery
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
CN108134116A (en) * 2017-12-26 2018-06-08 成都新柯力化工科技有限公司 A kind of poly- furfuryl alcohol modification fuel battery proton exchange film and its method of modifying
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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