CN100345332C - Process for preparing proton exchange film full cell chips with water retaining function - Google Patents
Process for preparing proton exchange film full cell chips with water retaining function Download PDFInfo
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- CN100345332C CN100345332C CNB2005100187409A CN200510018740A CN100345332C CN 100345332 C CN100345332 C CN 100345332C CN B2005100187409 A CNB2005100187409 A CN B2005100187409A CN 200510018740 A CN200510018740 A CN 200510018740A CN 100345332 C CN100345332 C CN 100345332C
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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
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- 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 a preparing method of a chip of a proton exchanging film fuel battery, which is characterized in that an inorganic nanoparticle water reserving layer is transferred to both sides of a proton exchanging film for preparing the chip of a fuel battery by using a transferring method, and the chip has water reserving performance. The preparing method comprises the processes that a catalyst layer is coated to the surface of a transferring medium, and the inorganic nanoparticle layer with a water reserving function is coated to the surface of the catalyst layer; the proton exchanging film is arranged between two transferring medium sheets coated with inorganic nanoparticles to be pressed with heat, the transferring medium is ripped away, and thus, the chip of a fuel battery is made. The prepared chip of a fuel battery has the excellent water reserving performance, and can work under a low humidifying condition and a high-temperature condition. In addition, the inorganic nanoparticle layer and the proton exchanging resin in the proton exchanging film are sufficiently linked in cross by the function of heat press. Thus, the combining strength between the inorganic nanoparticle layer and the proton exchanging film is increased.
Description
Technical field
The present invention relates to a kind of proton exchange film fuel cell chip is the preparation method of core components of PEMFC CCM (CatalystCoated Membrane), particularly has the preparation method of the fuel cell chip of better water retention property.
Background technology
Fuel cell is a kind of cleaning, efficient, the quiet electrochemical engine that moves.(ProtonExchange Membrane Fuel Cell PEMFC) has good application prospects in industries such as mobile communication equipment, portable electronics, national defence critical equipment, mechanical transports to Proton Exchange Membrane Fuel Cells.
Current, the operating temperature that improves Proton Exchange Membrane Fuel Cells has been subjected to people's common concern, because fuel cell is worked being higher than under 100 ℃ the condition, not only can simplify the aqueous water management system of PEMFC, and can improve the reactivity of catalyst such as platinum black, help improving the operating efficiency of fuel cell.The proton conduction of perfluoro sulfonic acid membrane needs the existence of water just can carry out, particularly when working temperature during greater than 100 ℃, the proton conductivity of film can reduce because of the dehydration of film, and the mechanical property of film also will descend simultaneously, the permeability of gas of inducing reaction increases, thereby influences fuel battery performance.Therefore be necessary to improve the water retention and the mechanical property of proton exchange membrane under hot conditions.
, carried out both at home and abroad heteropoly acid and perfluorinated sulfonic acid composite membrane, basic zirconium phosphate and perfluorinated sulfonic acid composite membrane, imidazoles drone salt or pyrazoles drone salt and perfluorinated sulfonic acid composite membrane for this reason, and inorganic oxide SiO
2, TiO
2, ZrO
2Deng with the research of inorganic-organic hybrid films such as perfluorinated sulfonic acid composite membrane.Studies show that dopen Nano SiO in the Nafion film
2The composite membrane that makes Deng inorganic nano-particle has water retaining function preferably under 100-130 ℃ of high temperature.The SiO that (2001) such as Mauritzt (1995) and Miyake are synthetic with original position
2Particle is diffused in the Nafion of swelling film and has made composite membrane.This film moisture content in the time of 120 ℃ is also higher, and proton conductivity approaches the level of Nafion film.But the SiO that mixes
2The phenomenon that content occurs successively decreasing to center membrane from the film surface.In EP0926754, the nanometer SiO that Arico Antonino and Antonucci Vincenzo then will synthesize in advance
2Powder is doped to blend film forming in the proton exchange resins solution.Nanometer SiO in this film
2Decentralization increases, and can also keep higher conductivity in the time of 145 ℃, but nanometer SiO
2Powder is easy to reunite in phase transition behavior takes place, and its particle diameter is difficult to control, and the mechanical strength of film also waits to improve.People such as Masahiro Watanabe (J.Electrochem.Soc, 1996,143,3847-3852) colloid that contains titanium oxide and Nafion resin solution double teeming film forming, made Nafion/TiO
2Composite membrane, but the particle diameter of titanium dioxide and decentralization all are difficult to control in the composite membrane.
The inorganic oxide (particle diameter 0.1～10 μ m) that [CN1442913A] such as the Mao Zongqiang of Tsing-Hua University will have moisture-keeping functions is coated in the both sides of handing over the matter exchange membrane, makes the composite membrane with self-moistening function.But, influence film fuel battery performance because film is met the solvent distortion seriously.In addition, compare with the nano particle inorganic oxide, the moistening effect of micro particles inorganic oxide is not best.Therefore, be necessary to carry out the research of inorganic matter or inorganic oxide nanoparticles moistening effect.
CCM (Catalyst Coated Membrane) is the fuel cell membrane electrode of a kind of novel framework of not growing up the nineties in last century, is the once technical revolution of fuel cell development.According to the definition of the US Fuel Cell Council (2000), CCM is meant among the PEMFC by proton exchange membrane and is coated in the catalyst/membrane assembly that the catalyst layer of its both sides constitutes.The whole electrochemical reaction of fuel cell is all finished on CCM, therefore is to realize the most crucial parts of fuel cell, and it is suitable that it acts on computer chip, and fuel cell chip therefore is otherwise known as.Compare with gaseous diffusion layer assembly (Catalyst CoatedGDL) with traditional catalyst, CCM has comparatively outstanding advantage:
1) functionalization that helps fuel cell module is distinguished.The notion of catalyst/gas diffusion layer assembly is overlapping with electrochemical reaction district (catalyst layer) and fuel delivery area (gas diffusion layers), is unfavorable for the diagnosis and the Analysis on Mechanism of assembly.
2) can improve the service efficiency of Pt, the Pt carrying capacity can be reduced to 0.2mg/cm
2Below, help reducing the cost of MEA.And in catalyst and the gaseous diffusion layer assembly, catalyst coated is on porous gas diffusion layer, and a large amount of catalyst enter the top layer of GDL, has caused the waste of Pt.Even GDL is carried out smooth processing or fine gradient design, the platinum carrying capacity also is difficult to be reduced to 0.2mg/cm
2Below, the assembly manufacturing cost significantly increases;
3) owing to improved the service efficiency of Pt, can make ultra-thinization of CCM catalyst layer, thickness＜5 μ m helps improving mass-transfer efficiency;
4) improve the interfacial structure of catalyst layer and proton exchange membrane, help keeping the unimpeded of proton channel, reduce the contact resistance of battery;
5) make GDL avoid the hydrophiling that causes because of the surface applied catalyst layer, help improving mass-transfer efficiency, reduce the concentration polarization of battery;
6) assembling is simple, is suitable for serialization and large-scale production, and need not and gas diffusion layers and hot binding, has reduced the damaged probability of proton exchange membrane, therefore can make ultra-thinization of proton exchange membrane, has helped reducing the film internal resistance of battery.
As seen, adopt the CCM technology, not only improved the electrochemical reaction activity of Catalytic Layer, but also can reduce the manufacturing cost of fuel cell.Simultaneously, how inorganic nano-particle water conservation technology is dissolved in the CCM technology, the CCM that preparation is worked under low-humidification or hot conditions is one of important directions of research both at home and abroad.
Summary of the invention
The invention provides a kind of preparation method of proton exchange film fuel cell chip, particularly inorganic nano-particle water conservation layer is transferred to the preparation of proton exchange membrane both sides and has the method for the fuel cell chip of water retention property by transfer medium.
The preparation method of a kind of proton exchange film fuel cell chip of the present invention, this method are transferred to the proton exchange membrane both sides by transfer method with inorganic nano-particle water conservation layer and prepare fuel cell chip, and its preparation process is followed successively by:
1) catalyst, proton exchange resins are mixed by 10: 2～5: 50～100 mass ratio is full and uniform with solvent, make catalyst slurry;
2) with SiO
2, TiO
2, Zr (HPO
4)
2Or ZrO
2The aqueous solution or colloidal solution fully mix with proton exchange resins solution, make the inorganic nano-particle slip, and wherein the inorganic nano-particle solid masses is than being 1wt%～20wt%;
3) adopt rubbing method or silk screen print method that the catalyst slurry of step 1 preparation is coated to the transfer medium PolytetrafluoroethylFilm Film, and dry, and polytetrafluoroethylene thickness 50～200 μ m, the thickness of catalyst layer are 1～5 μ m;
4) adopt with step 3 same procedure the inorganic nano-particle slip of step 2 preparation is coated to catalyst layer surface on the polytetrafluoroethylene film, the thickness of inorganic nano-particle water conservation layer is 1～5 μ m, the preparation coated film;
5) proton exchange membrane is placed in the middle of two coated film of step 4 preparation, wherein proton exchange membrane contacts with inorganic nano-particle water conservation layer, form three-in-one assembly, after the hot pressing, the inorganic nano-particle sublayer is transferred to the proton exchange membrane both sides with catalyst layer, peels off polytetrafluoroethylene film, promptly make proton exchange film fuel cell chip, wherein hot pressing temperature is 80～130 ℃, and the time is 1～5 minute, and pressure is 0.2～5MPa;
Described transfer medium is orientation or non-directional polytetrafluoroethylene film; Described catalyst is to be the Pt or the Pt alloy of carrier with carbon black, carbon nano-tube or carbon nano-fiber, or DNAcarrier free Pt or Pt alloy; Described proton exchange film resin is the perfluorinated sulfonic resin with sulfonic acid group, as the Nafion of du Pont company production
Resin, the Kraton G1650 resin that Dias company produces, or sulfonation thermal stability polymer, Flemion proton conductor polymer with proton exchange function; Described solvent is water or organic solvent alcohol, ether, ester, ketone, and wherein alcohol is methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycerol and 1-methoxyl group 2-propyl alcohol, and ether is ether, benzinum, and ester is an ethyl acetate, and ketone is acetone.
Described proton exchange membrane is the Nafion of perfluoro sulfonic acid membrane class
Film, Dow
Film, Flemion
Film, Aciplex
Film, the BAM3G film of the Ballard company of partially fluorinated proton exchange membrane class, sulfonated phenylethylene/butylene vinyl/styrene triblock copolymer the film (SEBS) of the Dais company exploitation of the proton exchange membrane class of nonfluorinated, and the polytetrafluoroethylene (PTFE) perforated membrane is the porous polymers base compound proton exchange membrane composite membrane of substrate, as Gore-select
TM
Pt alloy of the present invention is Pt
xM
yOr Pt
3M
xN
y, wherein x, y are respectively and are less than or equal to 3 natural number, and M, N are respectively the arbitrary metallic element among Pd, Ru, Rh, Ir, Os, Fe, Cr, Ni, Co, Mn, Cu, V, Ti, Ga, W, Sn, the Mo, and M and N are different.
The main component of inorganic nano-particle water conservation layer of the present invention is inorganic nano-particle and proton exchange resins.Inorganic nano-particle is SiO
2, TiO
2, Zr (HPO
4)
2Or ZrO
2Nano particle has water retention preferably usually, can prevent that fuel cell from descending because of the proton conductivity and the mechanical strength of film dehydration causing film down behind high temperature or long-play.
The present invention compares with background technology, and the fuel cell chip of preparation has better water retention performance, both can also can be worked under hot conditions under the low-humidification condition by its fuel battery assembled; In addition, owing to be subjected to hot pressing function, the crosslinking degree of the proton exchange resins in inorganic nano-particle sublayer and the proton exchange membrane is improved, so the adhesion between inorganic nano-particle sublayer and the proton exchange membrane is enhanced.
Description of drawings
Fig. 1 is the composition and the preparation skill worker figure of fuel cell chip of the present invention.
Monocell performance when Fig. 2 is 70 ℃ of battery temperatures.
Monocell performance when Fig. 3 is 120 ℃ of battery temperatures.
The number in the figure implication:
The 1-polytetrafluoroethylene film, 2-catalyst layer, 3-inorganic nano-particle sublayer, 4-proton exchange membrane;
A-polytetrafluoroethylene film 1, B-is at polytetrafluoroethylene film 1 surface applied catalyst layer 2, C-is in catalyst layer 2 surface applied inorganic nano-particle sublayers 3, D-places between two polytetrafluoroethylene films that are coated with inorganic nano-particle proton exchange membrane 4 and hot pressing, and E-throws off the fuel cell chip that makes behind the polytetrafluoroethylene film.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
According to Pt load amount is that the carbon of 40wt% carries Pt catalyst (U.S. Johnson Matthey company product): Nafion resin (DuPont company product): isopropyl alcohol is that 3: 1: 300 mass ratio prepares catalyst slurry, get the part slip, adopt silk screen print method to be printed onto-polytetrafluoroethylene film film surface, dry 1h, polytetrafluoroethylene film is the non-directional film, thickness 150 μ m.
SiO
2The preparation of nano particle slip: the tetraethoxysilane of 33ml and the absolute ethyl alcohol of 300ml are mixed, drip the absolute ethyl alcohol of 240ml and the mixed liquor of 0.3M hydrochloric acid 60ml then, under 50 ℃ temperature, continue to stir 12h, obtain containing nanometer SiO
2The aqueous solution.With nanometer SiO
2The aqueous solution and Nafion
Solution (the Nafion resin content is 5wt%, DuPont company product) mixes, ultrasonic 30min.If SiO
2And Nafion
The quality of resin is 100%, then SiO
2Proportion is 10wt%.
Adopt the SiO of silk screen print method with preparation
2The nano particle slip is coated in dry catalyst layer surface, dry 1h, and forming bed thickness in catalyst layer surface is the SiO of 2 μ m
2Nano particle water conservation layer.Place two to apply SiO Nafion 211 films
2Carry out hot-pressing processing between the film of nano particle water conservation layer, hot pressing temperature is 130 ℃, and the time is 2 minutes, and pressure is 0.6MPa, divests polytetrafluoroethylene film, makes CCM.
Monocell assembling and the performance test of CCM: diffusion layer adopts the carbon paper of hydrophobic treatment, PTFE content 30wt%, and the microporous layers of forming by PTFE and conductive carbon black (PTFE wraps up carbon black) at the compound one deck of one side (Micropore Layer), microporous layers is through 350 ℃ of calcining 20min down.Two collection plates are graphite cake, have parallel groove in a side.End plate is the copper facing stainless steel.Effective catalysis area of CCM is 5cm * 5cm.The monocell operating condition is: normal pressure, cathode and anode relative humidity are 50%, Pt carrying capacity 0.3mg/cm
2(anode 0.1mg/cm
2, negative electrode 0.2mg/cm
2).Monocell performance when 70 ℃ of battery temperatures and 120 ℃ is illustrated respectively among Fig. 2, Fig. 3.
Embodiment 2
The coating method of the preparation of catalyst slurry, catalyst slurry and inorganic nano-particle slip, the method for testing of monocell are identical with embodiment 1, and difference is that inorganic nano-particle is TiO
2, TiO
2The preparation method of slip is: add glacial acetic acid in butyl titanate, mix, slowly pour in the distilled water under vigorous stirring, continue to stir 2～6h, treat hydrolysis fully after, add the nitric acid of 70wt%, continue after being heated to 60～90 ℃ to stir 1～5h, make nano-TiO
2Colloidal solution.The volume ratio of above-mentioned additive is: butyl titanate: glacial acetic acid: distilled water: 70wt% nitric acid=1: 0.05～0.51～12.Then, with nano-TiO
2Colloidal solution and 5wt%Nafion
Solution mixes, ultrasonic 10min.If TiO
2And Nafion
The quality of resin is 100%, then TiO
2Proportion is 1wt%.Monocell performance when 70 ℃ of battery temperatures and 120 ℃ is illustrated respectively among Fig. 2, Fig. 3.
Embodiment 3
The coating method of the preparation of catalyst slurry, catalyst slurry and inorganic nano-particle slip, the method for testing of monocell are identical with embodiment 1, and difference is that inorganic nano-particle is Zr (HPO
4)
2, Zr (HPO
4)
2The preparation method of slip is: getting molar concentration is the basic zirconium chloride (ZrOCl of 1.5M
2) solution and absolute ethyl alcohol mix, and dropwise adds the mixed liquor that absolute ethyl alcohol and molar concentration are 1M phosphoric acid then, continues down to stir 1 2～24h at 60～90 ℃, obtains containing nanometer Zr (HPO
4)
2The aqueous solution.The volume ratio of above-mentioned additive is: 1.5M basic zirconium chloride: absolute ethyl alcohol: 1M phosphoric acid=1: 3～60: 0.05～1.Wherein 1/2 volume ethanol is mixed with zirconium oxychloride, and 1/2 volume ethanol is mixed with phosphoric acid in addition.To contain nanometer Zr (HPO
4)
2The aqueous solution and 5wt%Nafion
Solution mixes, ultrasonic 60min.If Zr (HPO
4)
2And Nafion
The quality of resin is 100%, then Zr (HPO
4)
2Proportion is 20wt%.Monocell performance when 70 ℃ of battery temperatures and 120 ℃ is illustrated respectively among Fig. 2, Fig. 3.
Embodiment 4
The coating method of the preparation of catalyst slurry, catalyst slurry and inorganic nano-particle slip, the method for testing of monocell are identical with embodiment 1, and difference is that inorganic nano-particle is ZrO
2, ZrO
2The preparation method of slip is: getting molar concentration is the basic zirconium chloride (ZrOCl of 1.5M
2) solution and ethanol solution, continue to stir 12～24h at 50～90 ℃, slowly pour distilled water into simultaneously, obtain containing nanometer ZrO
2The aqueous solution.The volume ratio of above-mentioned additive is: 1.5M basic zirconium chloride: absolute ethyl alcohol: distilled water=1: 3～60: 1～10.To contain nanometer ZrO
2The aqueous solution and 5wt%Nafion
Solution mixes, ultrasonic 30min.If ZrO
2And Nafion
The quality of resin is 100%, then ZrO
2Proportion is 10wt%.Monocell performance when 70 ℃ of battery temperatures and 120 ℃ is illustrated respectively among Fig. 2, Fig. 3.
Comparing embodiment 1
The preparation method of CCM and the method for testing of monocell are identical with embodiment 1, and difference is there is not the inorganic nano-particle sublayer among the CCM.Monocell performance when Fig. 2, Fig. 3 are respectively 70 ℃ of battery temperatures and 120 ℃.Under the low-humidification condition, the electrical property with CCM of inorganic nano-particle sublayer is better than not having the CCM of inorganic nano-particle sublayer.
Comparing embodiment 2
The method of testing of the preparation method of CCM, inorganic nano-particle slip and monocell is identical with embodiment 1, and difference is, preparation method's difference of inorganic nano-particle sublayer.Adopt silk screen print method directly the inorganic nano-particle slip to be coated in the proton exchange membrane both sides, and intensive drying, swelling set has taken place in film in the preparation process, and this is because the inorganic nano-particle slip contains water and pure equal solvent, and proton exchange membrane has the characteristic of meeting the solvent swell distortion.Monocell performance when 70 ℃ of battery temperatures and 120 ℃ is illustrated respectively among Fig. 2, Fig. 3.Be not difficult to find out that under the low-humidification condition, the electrical property of the CCM of the present invention's preparation is better than the CCM that direct coating process prepares the inorganic nano-particle sublayer.
Claims (1)
1, a kind of preparation method of proton exchange film fuel cell chip, this method is transferred to the proton exchange membrane both sides by transfer method with inorganic nano-particle water conservation layer and prepares fuel cell chip, it is characterized in that these chip both sides from outward appearance to inner essence are catalyst layer-inorganic nano-particle and proton exchange resins articulamentum-proton exchange membrane, preparation process is followed successively by:
1) catalyst, proton exchange resins are mixed by 10: 2～5: 50～100 mass ratio is full and uniform with solvent, make catalyst slurry;
2) with SiO
2, TiO
2, Zr (HPO
4)
2Or ZrO
2The inorganic nano-particle aqueous solution or colloidal solution fully mix with proton exchange resins solution, make the inorganic nano-particle slip, and wherein the solid masses of inorganic nano-particle is than being 1wt%～20wt%;
3) adopt rubbing method or silk screen print method that the catalyst slurry of step (1) preparation is coated to the transfer medium PolytetrafluoroethylFilm Film, and dry, and polytetrafluoroethylene thickness 50～200 μ m, the thickness of catalyst layer are 1～5 μ m;
4) adopt with step (3) same procedure the inorganic nano-particle slip of step (2) preparation is coated to catalyst layer surface on the polytetrafluoroethylene film, the preparation coated film, the thickness of inorganic nano-particle water conservation layer is 1～5 μ m;
5) proton exchange membrane is placed in the middle of two coated film of step (4) preparation, wherein proton exchange membrane contacts with inorganic nano-particle water conservation layer, form three-in-one assembly, after the hot pressing, the inorganic nano-particle sublayer is transferred to the proton exchange membrane both sides with catalyst layer, peels off polytetrafluoroethylene film, promptly make proton exchange film fuel cell chip, wherein hot pressing temperature is 80～130 ℃, and the time is 1～5 minute, and pressure is 0.2～5MPa;
Wherein said transfer medium is orientation or non-directional polytetrafluoroethylene film; Described catalyst is to be the Pt or the Pt alloy of carrier with carbon black, carbon nano-tube or carbon nano-fiber, or DNAcarrier free Pt or Pt alloy; Described proton exchange film resin is the Nafion with perfluorinated sulfonic resin class of sulfonic acid group
Resin, the Kraton G1650 resin that Dias company produces, or sulfonation thermal stability polymer, Flemion proton conductor polymer with proton exchange function; Described solvent is water or organic solvent alcohol, ether, ester, ketone, and wherein alcohol is methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycerol and 1-methoxyl group 2-propyl alcohol, and ether is ether, benzinum, and ester is an ethyl acetate, and ketone is acetone.
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| CN100345332C true CN100345332C (en) | 2007-10-24 |
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| CN100384001C (en) * | 2006-04-28 | 2008-04-23 | 华南理工大学 | Direct spraying method for preparing fuel cell membrane electrode |
| CN101350409B (en) * | 2007-07-18 | 2010-12-08 | 比亚迪股份有限公司 | Method for preparation of membrane electrode of proton exchange film fuel cells |
| CN102268690B (en) * | 2011-06-15 | 2014-01-29 | 天津大学 | Diaphragm for electrochemical synthesis of dinitrogen pentoxide and preparation method thereof |
| CN102800881B (en) * | 2012-08-03 | 2016-08-31 | 上海锦众信息科技有限公司 | A kind of preparation method of fuel cell inorganic proton exchange film |
| CN104779401B (en) * | 2015-03-23 | 2017-01-11 | 山东德汇新能源科技发展有限公司 | Method for plating metal elements on nano porous metal film |
| CN108011109B (en) * | 2017-11-29 | 2021-04-23 | 中国科学技术大学 | Preparation method of membrane electrode and fuel cell |
| CN108011120B (en) * | 2017-11-29 | 2021-04-23 | 中国科学技术大学 | Preparation method of membrane electrode |
| US20190317042A1 (en) * | 2018-04-13 | 2019-10-17 | Honeywell International Inc. | Systems and methods for a printed electrochemical gas sensor |
| CN109088073A (en) * | 2018-07-13 | 2018-12-25 | 东莞众创新能源科技有限公司 | Proton Exchange Membrane Fuel Cells ccm membrane electrode and preparation method thereof |
| CN112599793B (en) * | 2020-12-14 | 2022-07-19 | 中国科学院大连化学物理研究所 | CCM coating process for realizing anti-swelling by using protective back membrane |
| CN112599791B (en) * | 2020-12-14 | 2022-05-17 | 中国科学院大连化学物理研究所 | High-yield fuel cell catalytic electrode coating production method and equipment thereof |
| CN112599796B (en) * | 2020-12-14 | 2021-11-02 | 中国科学院大连化学物理研究所 | Fuel cell electrode CCM batch production method and equipment thereof |
| CN112599794B (en) * | 2020-12-14 | 2022-04-15 | 中国科学院大连化学物理研究所 | Batch preparation method and equipment for high-yield catalytic electrode of fuel cell |
| CN113903939A (en) * | 2021-09-27 | 2022-01-07 | 中汽创智科技有限公司 | Proton exchange membrane and preparation method thereof |
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