CN108878993A - A method of slowing down proton exchange membrane electrochemical degradation - Google Patents
A method of slowing down proton exchange membrane electrochemical degradation Download PDFInfo
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- CN108878993A CN108878993A CN201710333243.0A CN201710333243A CN108878993A CN 108878993 A CN108878993 A CN 108878993A CN 201710333243 A CN201710333243 A CN 201710333243A CN 108878993 A CN108878993 A CN 108878993A
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- 239000012528 membrane Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000015556 catabolic process Effects 0.000 title claims abstract description 12
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 12
- 150000003254 radicals Chemical class 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 238000006277 sulfonation reaction Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 10
- 239000003456 ion exchange resin Substances 0.000 claims description 10
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 10
- 239000002105 nanoparticle Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 229920000557 Nafion® Polymers 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229940113088 dimethylacetamide Drugs 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229920002490 poly(thioether-sulfone) polymer Polymers 0.000 claims description 3
- 229920002480 polybenzimidazole Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 230000001680 brushing effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 102000004895 Lipoproteins Human genes 0.000 claims 1
- 108090001030 Lipoproteins Proteins 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229920001429 chelating resin Polymers 0.000 claims 1
- 125000005909 ethyl alcohol group Chemical group 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 abstract description 3
- 239000005518 polymer electrolyte Substances 0.000 abstract 1
- 238000005266 casting Methods 0.000 description 5
- 150000002484 inorganic compounds Chemical class 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 238000002144 chemical decomposition reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012028 Fenton's reagent Substances 0.000 description 2
- 230000003026 anti-oxygenic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007590 electrostatic spraying Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
Abstract
The present invention relates to one kind to slow down proton exchange membrane electrochemical degradation method, this method in proton exchange membrane by adding free radical quencher, prepare organic/inorganic compoiste proton exchange film, under the premise of guarantee proton exchange membrane high conductivity, the electrochemical stability of film is improved, this composite membrane shows preferable stability in fuel cell and polymer electrolyte water electrolysis pond.
Description
Technical field
The invention belongs to ion-exchange resin technique fields more particularly to one kind to slow down proton exchange membrane electrochemical degradation
Method.
Background technique
Proton exchange membrane (PEM) as a kind of functional high-polymer with compared with high ionic conductivity and chemical stability,
It is widely used to energy storage and conversion field at present.Wherein, fuel cell and polymer dielectric (SPE) water electrolytic cell are
Proton exchange membrane is used successfully to the Typical Representative of new energy field.Fuel cell due to its energy conversion efficiency is high, specific power is high,
Advantages of environment protection has broad application prospects in terms of onboard power power supply and mobile power supply；And SPE water electrolysis
Hydrogen producing technology has mild operating condition, quick response and performance stabilization etc. excellent compared to traditional fossil fuel hydrogen manufacturing
Point becomes current noticeable hydrogen producing technology.Critical material as these clean energy technologies --- proton exchange membrane is removed
It wants outside ionic conductivity with higher, electrochemical stability is also the factor for having to consider.Because proton exchange membrane
Stability directly decides fuel cell and SPE water electrolytic cell long-term running service life.
Under study for action, the degradation of proton exchange membrane mainly includes mechanical degradation, thermal degradation and chemical degradation, wherein chemistry
Degradation is the principal degradation mode of proton exchange membrane in longtime running.For the chemical degradation of PEM, in fuel battery operation,
The infiltration of reaction gas, the dissolution of catalyst platinum and redeposited, many such as generation of transition metal ions impurity and free radical
Factor can all cause the chemical degradation of film；And under the conditions of water electrolysis, it is often associated with H2O2Generation, when transition metal ions with
H2O2When coexisting, H2O2The free radicals such as easy decomposing H O&HOO, attack proton exchange membrane.Chemical degradation master is generally believed at present
If free radical (HO&HOO) is attacked caused by the main chain or side chain of polymer film.Therefore, the chemistry of proton exchange membrane is improved
Stability becomes a highly important project.
For the decaying for slowing down proton exchange membrane, its chemical stability is promoted, there are mainly two types of means：(1) press down on source
The generation of free radical processed；(2) free radical of generation is quenched in time.Curtin et al. (Journal of Power Sources,
2004.131.41) by carrying out the content that processing reduces the end group containing H in PEM to PEM, and then improve the stability of PEM；China
Xiao of Dalian Chemical Physics Research Institute of the academy of sciences et al. (Chinese patent：CN 102479956) by the microcosmic of proton exchange membrane
Pattern is modified, and improves the chemical stability of film well.The above method, which is concentrated mainly on, inhibits free radical to generate, and not
The free radical of generation is quenched.The chemistry of PEM is promoted surely by into proton exchange membrane, being directly added into free radical quencher
Qualitative is a kind of simple and easy, and highly effective method.
Free radical quencher is added in present invention selection in proton exchange membrane, prepares organic/inorganic compound film, and then promoted
The electrochemical stability of PEM makes it be preferably applied for fuel cell and SPE water electrolytic cell.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for slowing down proton exchange membrane electrochemical degradation.
Technical scheme is as follows：
One kind slowing down proton exchange membrane electrochemical degradation method, is mainly quenched by adding free radical into proton exchange membrane
It goes out agent, prepares organic/inorganic compoiste proton exchange film, concrete operation step is as follows：
(1) resin solution will be prepared containing the dissolution of sulfonic ion exchange resin in a solvent；
(2) in the resin solution that the nano particle of free radical quencher is added, ultrasonic disperse is uniform；
(3) resin solution that free radical quencher is added is cast in horizontal glass plate, the solvent flashing in drying box
Film forming.
(4) or in the both side surface of proton exchange membrane the nanoparticle layers of one layer of free radical quencher are prepared respectively；
(5) one layer of sulfonic ion exchange resin layer is being sprayed on the nanoparticle layers in (4) again, preparation is multiple layer by layer
Close film.
The free radical quencher added in proton exchange membrane includes ceria, manganese dioxide, in di-iron trioxide
It is one or more kinds of；The adding method of free radical quencher is to be blended, compound layer by layer.
Contain sulfonic ion exchange resin used in step (1), mainly includes：Perfluorinated sulfonic resin (commercialization
Nafion), the polyether-ether-ketone (SPEEK) of sulfonation, the polyimides (SPI) of sulfonation, sulfonation polybenzimidazoles (SPBI), sulphur
Change one of poly thioether sulfone (SPSSF) sulfonation benzodiazine polyethersulfone ketone (SPPESK) or two kinds or more；.
Solvent used in step (1) be ethyl alcohol, normal propyl alcohol, isopropanol, water, dimethylformamide, dimethyl acetamide,
One or more of methyl pyrrolidone；The concentration for preparing resin solution is 1%-50% (mass fraction).
The nano particle diameter range of the free radical quencher of addition in step (2) is 5-60 nanometers；Free radical is quenched
The additive amount of agent is 0.02-0.15 times of sulfonate resin quality.
Its drying temperature of drying box used in step (3) is 80-150 DEG C；Drying time is 8-72 hours.
The preparation method of layer is quenched as brushing, electrostatic spraying etc. in free radical in step (4)；The loading of quencher is
0.05-0.1 milligrams every square centimeter.
The preparation method of sulfonic ion exchange resin is to brush in step (5), electrostatic spraying etc.；Quencher supports
Amount is every square centimeter for 0.1-1.0 milligrams.
Free radical quencher is added in present invention selection in proton exchange membrane, prepares organic/inorganic compound film, and then promoted
The electrochemical stability of PEM makes it be preferably applied for fuel cell and SPE water electrolytic cell.
Detailed description of the invention
Fig. 1 is that organic/inorganic compound film prepared by the embodiment of the present invention 1 is different from the PEM for being not added with free radical quencher
Conductivity Ratio is relatively schemed under the conditions of temperature.
Fig. 2 is organic/inorganic compound film and be not added with the PEM of free radical quencher in matter prepared by the embodiment of the present invention 1
Open-circuit voltage changes over time figure in proton exchange film fuel cell.
Fig. 3 is that organic/inorganic compound film prepared by the embodiment of the present invention 2 exists with the PEM for being not added with free radical quencher
The quality retention rate tested in Fenton reagent changes over time figure.
Specific embodiment
In conjunction with following embodiment, the invention will be further described, but embodiment is illustrative, and non-limiting
, it cannot be limited the scope of protection of the present invention with following embodiment.
Embodiment 1
The partial solvent evaporation of 5wt%Nafion solution is made to the Nafion solution of 20wt%.1gSPEEK is taken to be dissolved in 3g
In dimethyl acetamide, the 20wt%Nafion solution of 1.25g is added, is stirred at room temperature to being completely dissolved, SPEEK/ is made
Nafion solution (mass ratio SPEEK:Nafion=4:1).A certain amount of SPEEK/Nafion solution is taken, whole quality point is added
The CeO of number 0.5wt%2Powder, wherein CeO2Average grain diameter be 14 nanometers, 2h, ultrasonic 1h is mixed, and it is quiet at room temperature
It sets 5h removing bubble and prepares CeO to avoid defect is generated in film forming procedure2The casting solution of/ion exchange resin.It will prepare
On the casting solution to the horizontal glass plate of 9 × 11cm size got well, dried for 24 hours in 80 DEG C of drying boxes.
Using above-mentioned identical method, it is different from place and is not add free radical quencher CeO2, prepare and do not add
The PEM of free radical quencher.Two kinds of films of preparation are tested into its ionic conductivity at different temperatures, as shown in Figure 1, result
After display addition free radical quencher, though the proton conductivity of PEM compares and the PEM of quencher is not added decreases, to occur
Sharp fall；In the open-circuit voltage test of Proton Exchange Membrane Fuel Cells, result is as shown in Fig. 2, show addition freely
The PEM of base quencher shows preferable stability test.
Embodiment 2
Prepare casting solution slurry：Weighing the dry SPBI resin of 0.2244g, to be dissolved in 18g N-Methyl pyrrolidone (NMP) molten
In agent, stirring is completely dissolved to SPBI, is filtered to remove impurity.Then the CeO of mass fraction 2wt% is added2Powder, wherein CeO2
The average grain diameter of nanoparticle is 7 nanometers, and 2h, ultrasonic 1h is mixed, and stands 5h at room temperature and remove bubble, is obtained
SPBI-CeO2Casting solution.Casting solution is cast in the horizontal glass plate of 9 × 11cm size, it is dry in 100 DEG C of drying boxes
24h.Obtain CeO2Load amount is 2wt%SPBI-CeO2Composite membrane.
Using above-mentioned identical method, it is different from place and is not add free radical quencher CeO2, prepare and do not add
The proton exchange membrane of free radical quencher --- SPBI.Two kinds of films of preparation are tested into its inoxidizability in Fenton reagent
Can, as shown in figure 3, the antioxygenic property of composite membrane is substantially better than pure SPBI film after adding free radical quencher as the result is shown,
CeO2Addition facilitate the promotion of composite membrane antioxygenic property.
Claims (10)
1. one kind slows down proton exchange membrane electrochemical degradation method, mainly it is quenched by adding free radical into proton exchange membrane
Agent, prepares organic/inorganic compoiste proton exchange film, and the adding method of free radical quencher is blending or compound layer by layer, tool
Steps are as follows for gymnastics work：
It is blended：
(1) resin solution will be prepared containing the dissolution of sulfonic ion exchange resin in a solvent；
(2) in the resin solution that the nano particle of free radical quencher is added, ultrasonic disperse is uniform；
(3) resin solution that free radical quencher is added is cast in horizontal glass plate, drying and volatilizing solvent film forming；Must have
Machine/inorganic compoiste proton exchange film；
Or it is compound layer by layer, A, the nanoparticle of one layer of free radical quencher is prepared respectively in the both side surface of proton exchange membrane
Layer；
B, one layer of sulfonic ion exchange resin layer is being sprayed on the nanoparticle layers in A again, it is compound layer by layer to prepare proton
Exchange membrane.
2. preparation method according to claim 1, it is characterised in that：The free radical quencher added in proton exchange membrane
Including one or more of ceria, manganese dioxide, di-iron trioxide.
3. preparation method according to claim 1, it is characterised in that：Contain sulfonic ion used in step (1)
Exchanger resin mainly includes：Perfluorinated sulfonic resin (commercialized Nafion), the polyether-ether-ketone (SPEEK) of sulfonation, sulfonation it is poly-
Acid imide (SPI), the polybenzimidazoles (SPBI) of sulfonation, sulfonated poly thioether sulfone (SPSSF) sulfonation benzodiazine polyethersulfone ketone
Or two kinds or more one of (SPPESK).
4. preparation method according to claim 1, it is characterised in that：Solvent used in step (1) be ethyl alcohol, positive third
Alcohol, isopropanol, water, dimethylformamide, dimethyl acetamide, one or more of methyl pyrrolidone；Prepare tree
The concentration of lipoprotein solution is 1%-50% (mass fraction).
5. preparation method according to claim 1,2 or 3, it is characterised in that：The free radical of addition in step (2) is quenched
The nano particle diameter range of agent is 5-60 nanometers；The additive amount of free radical quencher is to contain sulfonic ion exchange resin
0.02-0.15 times of quality.
6. preparation method according to claim 1, it is characterised in that：Drying temperature used in step (3) is 80-150
℃；Drying time is 8-72 hours.
7. preparation method according to claim 1 or 2, it is characterised in that：Free radical quencher is dissolved in solvent by step A
In, prepare free radical quencher solution；The preparation method of layer is quenched as brushing, electrostatic in nanoparticle layers free radical in step A
One or more of apply etc., drying and volatilizing solvent film forming；The loading of free radical quencher is 0.05-0.1 milligrams every
Square centimeter.
8. preparation method according to claim 1 or 3, it is characterised in that：Step B will contain sulfonic amberlite
Liposoluble solution in a solvent, prepares resin solution；The preparation method of sulfonic ion exchange resin layer is to brush in step B, quiet
One or more of electrospray etc., drying and volatilizing solvent film forming；The loading of quencher is 0.1-1.0 milligrams every square
Centimetre.
9. preparation method according to claim 7 or 8, it is characterised in that：Solvent used in step A or B is ethyl alcohol, just
Propyl alcohol, isopropanol, water, dimethylformamide, dimethyl acetamide, one or more of methyl pyrrolidone；It prepares
The concentration of resin solution is 1%-50% (mass fraction), and the mass concentration of quencher is 0.1%-10%；
Drying temperature is 80-150 DEG C in step A or B；Drying time is 8-72 hours.
10. preparation method according to claim 7 or 8, it is characterised in that：The resin that proton exchange membrane uses in step A
Material includes：Perfluorinated sulfonic resin (commercialized Nafion), the polyether-ether-ketone (SPEEK) of sulfonation, sulfonation polyimides
(SPI), the polybenzimidazoles (SPBI) of sulfonation, sulfonated poly thioether sulfone (SPSSF) sulfonation benzodiazine polyethersulfone ketone (SPPESK)
One of or two kinds or more；Or proton exchange membrane is the proton exchange containing free radical quencher of step (3) preparation in step A
Film.
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| CN112582657A (en) * | 2020-12-14 | 2021-03-30 | 中国科学院大连化学物理研究所 | Preparation method of ultrathin proton exchange composite membrane with high proton conductivity |
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| CN112652795A (en) * | 2020-12-14 | 2021-04-13 | 南京大学 | Composite proton exchange membrane of fuel cell and preparation method thereof |
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| CN113690450A (en) * | 2021-08-25 | 2021-11-23 | 中汽创智科技有限公司 | Free radical quenching agent, preparation method thereof and application thereof in membrane electrode |
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| CN114464853A (en) * | 2022-01-27 | 2022-05-10 | 六创资源环境研究院(南京)有限公司 | Preparation method of non-fluorine proton exchange membrane with high chemical stability |
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