CN100428544C - Producing method for proton exchange film fuel cell pole and membrance electrode - Google Patents
Producing method for proton exchange film fuel cell pole and membrance electrode Download PDFInfo
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- CN100428544C CN100428544C CNB2006101136470A CN200610113647A CN100428544C CN 100428544 C CN100428544 C CN 100428544C CN B2006101136470 A CNB2006101136470 A CN B2006101136470A CN 200610113647 A CN200610113647 A CN 200610113647A CN 100428544 C CN100428544 C CN 100428544C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
This invention relates to a method for preparing proton exchange membrane fuel batteries and membrane electrodes including A, preparing catalyst serum, mixing a polymer electrolyte solution, de-ionic water and first primary group alkali metal hydrate or its salt compound solution, adding PtRu black anode electric catalyst into said solution to be mixed uniformly to get an anode catalyst serum, adding Pt black cathode catalyst into the solution to be mixed uniformly to get a cathode catalyst serum, B, preparing electrode of fuel batteries to scatter and deposit the catalyst solution onto the films of conduction base, the conduction proton base or non-conduction base, which can effectively avoid conglobation caused by the static action among polymer electrolyte sulfonic acid groups by adding a first primary group alkali metal hydrate or other salt compound solutions and the polymer electrolyte and catalyst components can be scattered uniformly in the catalyst solution.
Description
Technical field
The present invention relates to a kind of preparation method of fuel cell electrode, relate in particular to a kind of proton exchange membrane fuel cell electrode and membrane electrode preparation method.
Background technology
Proton Exchange Membrane Fuel Cells is that a class is the electrolytical electrochemical reaction appts that the chemical energy of fuel is directly changed into electric energy with perfluoro sulfonic acid membrane.When fuel is hydrogen, be called hydrogen-oxygen proton exchange membrane fuel cell (PEMFC); When fuel is pure time-likes such as methyl alcohol, ethanol, be called direct alcohol fuel battery (DAFC).This types of fuel cells has theoretical energy density height, advantages of environment protection, has broad application prospects at aspects such as communications and transportation, underwater robot, home-use dispersion power station, consumer electronic product, compact power, military removable power supplys.
Membrane electrode assembly (MEA) is the core component of PEMFC and DAFC.Its performance and eelctro-catalyst activity, electrode and MEA structure etc. are all multifactor relevant.Catalyst slurry, electrode and MEA preparation method all have considerable influence to the microstructure of MEA.The PEMFC electrode preparation has been used for reference electrode preparation method in the phosphoric acid fuel cell (PAFC) at first, it promptly is the porous diffusion electrode of binding agent with the polytetrafluoroethylene (PTFE), by high temperature high pressure process catalyst is penetrated in the dielectric film so that Catalytic Layer has certain proton conductivity, but because the Catalytic Layer that electrolyte can not enter electrode, can't set up proton channel in the pole catalyze layer, electrochemical reaction only can be located to carry out in film/electro-catalysis bed boundary, thereby catalyst utilization is lower.The successful exploitation of solubility Nafion polymer also is incorporated into electrode interior by the mode at electrode surface dipping and has significantly improved catalyst utilization (document 1), the noble metal carrying capacity has reduced nearly order of magnitude, but the polymer impregnated degree of depth of Nafion is difficult to and Catalytic Layer thickness coupling among this preparation technology.People such as Wilson have been developed a kind of improved preparation technology (document 2) on this basis.In catalyst slurry, remove PTFE fully, add the Nafion polymer.Evenly mix with catalyst granules by dried Nafion polymer, so the polymer impregnated degree of depth of Nafion and Catalytic Layer thickness can mate preferably.Electrode preparation mainly is to adopt above-mentioned preparation method based on the slurries process among PEMFC and the DAFC at present, for example: use loaded PtRu/C or non-supported PtRu black as anode catalyst, use loaded Pt/C or non-supported Pt black as cathod catalyst, water and/or various organic solvent are as dispersant, and the Nafion polymer is mixed with catalyst slurry as binding agent and proton conductor.Then it is directly disperseed/is deposited on to form pole catalyze layer on dielectric film surface or the diffusion layer surface.The form of Nafion polymer influences the way of contact between itself and the catalyst.The Nafion polymer is reunited in solution in two ways, and a kind of is to assemble to form once by its carbon fluorine main chain to reunite, and another kind is to assemble by the electrostatic interaction between the sulfonate group of side chain to form secondary agglomeration.Owing to adopt water and/or organic solvent in the existing catalyst slurry technology of preparing as dispersant, there are above two kinds of reunion modes simultaneously in the Nafion polymer in these solvents, dispersed relatively poor in catalyst slurry of catalyst and Nafion polymer, Zhi Bei electrode catalyst utilance is lower thus.
Document 1[US 4876115] to introduce following method and prepared gas-diffusion electrode: the slurries that loaded platinum catalyst and polymer bonding agent (as PTFE) are formed deposit to the substrate of conduction (as carbon paper, the diffusion layer of preparation such as carbon cloth) on, then the Nafion polymer solution is sprayed to this electrode surface, remove organic solvent by methods such as heat treatments, form porous gas diffusive electrode.Nafion polymer depth and Catalytic Layer thickness owing to spraying in this method can not finely mate usually, the Nafion polymer is difficult to fully contact with eelctro-catalyst, fuel and oxidant produce in catalyst surface generation electrochemical reaction when battery operated proton, electronics and CO
2Deng can not transmitting timely and effectively, move, thereby the utilance of catalyst is lower, usually less than 30%.
Document 2[USP 5234777] method having introduced preparation catalyst slurry among the PEMFC and prepared MEA.This method as binding agent and catalyst mix, adopts the mixed solvent of water and glycerine to prepare catalyst slurry as dispersant in a certain amount of Nafion polymer.Then catalyst slurry is brushed or cast in the Teflon substrate, be used separately as anode and cathode catalysis layer.Anode and cathode catalysis layer are placed the dielectric film both sides respectively, Catalytic Layer is transferred to the MEA that forms sandwich structure on the dielectric film by hot pressing.Perhaps the cathode and anode catalyst slurry is cast straight to the dielectric film both sides respectively and forms the film (CCM) that is covered with catalyst.This technology directly is mixed with slurries with catalyst and Nafion polymer solution, and both contact better, compares with document 1, and catalyst utilization is greatly improved.Yet because the glycerine boiling point is about 290 ℃, not volatile at normal temperatures, solvent flashing easily causes Catalytic Layer embrittlement under the high temperature, has influence on transmission, the migration of electronics in the electrode, proton, and then can influence battery performance.
Document 3[J.Electrochem.Soc.142 (1995) 463-468] in introduced a kind of method of the Nafion of use polymeric colloid formulations prepared from solutions electrode.When the dielectric constant of solvent was between 3＜ε＜10, the Nafion polymer was colloidal state in this solvent.During the preparation catalyst slurry Nafion polymer dispersed is arrived dielectric constant in the solvent of 3＜ε＜10 scopes, in butyl acetate, add catalyst again and form catalyst slurry.This method helps the Nafion polymer and form network configuration in Catalytic Layer, has improved proton conductivity.Yet selected butyl acetate equal solvent toxicity is bigger.
Document 4[WO 02/45188A2] introduced the preparation method of catalyst slurry liquid making method among the DAFC and MEA.This method adopts water to prepare catalyst slurry as dispersant.Catalyst slurry places ice-water bath in the electrode production process, sonic oscillation, and spraying or brushing are on Teflon substrate or Nafion film or diffusion layer.Water is cheap for organic solvent, and environmental friendliness has certain advantage as solvent.But because water is unfavorable for the dispersion of catalyst and Nafion polymer as solvent, the catalyst slurry fluid viscosity is bigger, is easy to plug nozzle, is unfavorable for the carrying out that sprays.
Summary of the invention
The object of the present invention is to provide a kind of proton exchange membrane fuel cell electrode and membrane electrode preparation method.
For achieving the above object, technical scheme of the present invention is: by in catalyst slurry, adding alkali-metal hydroxide of first main group or its esters compound solution, form that alkali metal ion surrounds with-SO
3 -Be the ionic atmosphere at center, effectively shielded sulfonate group (SO in the polymer dielectric
3H) electrostatic interaction between, avoided the secondary agglomeration of polymer dielectric, component such as polymer dielectric and catalyst is evenly disperseed in the catalyst slurry, catalyst fully contacts with polymer dielectric in the electrode of preparation, thereby the performance of catalyst utilization and battery all is significantly improved.
Put it briefly, the method for making of Proton Exchange Membrane Fuel Cells of the present invention and direct alcohol fuel battery electrode and membrane electrode, step is as follows:
A) preparation catalyst slurry
The first step, the dispersion of polymer dielectric: polymer dielectric solution, deionized water and the first main group alkali metal hydroxide or its esters compound solution are mixed;
In second step, catalyst mixes with the polymer dielectric solution of dispersion: anode electrocatalyst is joined in the solution that is prepared by the first step, mix, obtain the anode catalyst slurries;
Electrocatalyst for cathode is joined in the solution that is prepared by the first step, mix, obtain the cathod catalyst slurries;
Described anode electrocatalyst is: Pt/C, Pt
3Sn/C, PtRu/C, Pt
3W/C or PtRu are black;
Described electrocatalyst for cathode is: Pt
3Cr/C, Pt
3Fe/C, Pt
3Co/C, Pt/C, Pt
3Pd/C or Pt are black;
B) electrode of preparation fuel cell: catalyst slurry disperses/deposits to conductive substrates, leads on proton substrate or the non-conductive substrate film.
Described method for making, wherein, the alkali-metal hydroxide solution of first main group is NaOH, KOH, Na
2SO
4, K
2SO
4, NaCl or KCl solution.
Described method for making, wherein, polymer dielectric is a solid electrolyte.
Described method for making, wherein, polymer dielectric is Nafion polymer or Flemion polymer.
Described method for making wherein, adds monohydric alcohol or ethylene glycol organic solvent after second step of steps A.
Described method for making, wherein, organic solvent is ethanol or isopropyl alcohol.
Described method for making, wherein, substrate film is porous gas diffusion layer, proton exchange membrane, polytetrafluoroethylene (PTFE) film.
The present invention mixes polymer dielectric solution, deionized water and the first main group alkali metal hydroxide or its esters compound solution, form that alkali metal ion surrounds with-SO
3 -Be the ionic atmosphere at center, effectively sulfonate group (SO in the shielded polymer electrolyte
3H) electrostatic interaction between is avoided the reunion of polymer dielectric, thereby polymer dielectric is evenly disperseed.
Compared with prior art, catalyst electrode preparation method of the present invention has the following advantages:
(1) each component of helping in the catalyst slurry of electrode preparation method of the present invention is evenly disperseed: existing catalyst slurry liquid and preparation method thereof is owing to adopt Hydrogen polymer dielectric solution (as Nafion solution), water and/or organic solvent, polymer dielectric is easily reunited, and is little with the catalyst contact area.And among the present invention by in polymer dielectric solution, adding alkali-metal hydroxide of first main group or its esters compound solution, form that alkali metal ion surrounds with-SO
3 -Be the ionic atmosphere at center, effectively sulfonate group (SO in the shielded polymer electrolyte
3H) reunion of polymer dielectric is avoided in the interaction between, makes evenly disperseing in catalyst slurry of polymer dielectric and catalyst.
(2) catalyst utilization in the electrode improves: the electrode of the inventive method preparation more helps contacting between catalyst and the polymer dielectric, and the utilance of catalyst is improved.
Description of drawings
Fig. 1 a and Fig. 1 b are respectively the Hydrogen among the embodiment 1 and add the particle size distribution figure of the Nafion polymer in the Nafion polymer solution of NaOH solution.
Fig. 2 is the performance curve that embodiment 2 and embodiment 3 adopt the Hydrogen and the catalyst slurry gained membrane electrode of the Nafion polymer solution preparation that adds NaOH respectively, and operating condition: battery temperature is 75 ℃; 1mol/L methanol aqueous solution 1ml/min sample introduction; 0.2MPa oxygen, flow velocity are 3.3ml/s.
Fig. 3 is the electrode anode polarization curve of embodiment 2 (employing water is solvent) and embodiment 4 (adopting pure water mixed solvent) preparation.
Fig. 4 is embodiment 5 (adopting the PTFE film is the substrate preparation pole catalyze layer) and embodiment 6
(adopting diffusion layer is the substrate preparation pole catalyze layer) membrane electrode performance curve, operating condition is with embodiment 1.
Embodiment
In order to further specify the present invention, enumerate following examples, do not limit scope of invention.
The Nafion polymer Hydrogen and the present invention add in the Nafion polymer solution of NaOH dispersion effect relatively.
The Nafion polymer solution and the Hydrogen Nafion polymer solution that prepare the adding NaOH dispersion of same concentrations respectively, the particle size distribution of the Nafion polymer in two kinds of solution of employing dynamic light scattering technical testing.
(1) the Nafion polymer solution of adding NaOH: (SE-5142, Dupont) solution add deionized water 1600mg to 400mg 5%Nafion, add 300mg 0.5M NaOH solution again, ultrasonic mixing.
(2) Hydrogen Nafion polymer solution: (SE-5142 Dupont), adds the 1900mg deionized water to 400mg 5%Nafion solution.Ultrasonic mixing.
Test the particle size distribution of the Nafion polymer in the above-mentioned Nafion polymer solution with dynamic light scattering method.The results are shown in Figure 1a and Fig. 1 b.Nafion polymer particle diameter in the solution that the adding NaOH that as can be seen from the figure adopts in the inventive method disperses is less, the particle size distribution of 75% Nafion polymer is between 20-40nm, and the particle of Nafion polymer is bigger in the Nafion solution of Hydrogen, the particle size distribution of the Nafion polymer more than 70% is more than 200nm, explanation is in Hydrogen solution, and the Nafion molecule is reunited easily becomes bigger particle.In the Nafion polymer solution of the adding NaOH of method preparation of the present invention, Nafion polymer particle diameter is less, illustrates that this method helps the dispersion of Nafion polymer in solution.
Embodiment 2
Electrode and MEA performance membrane electrode preparation process that the Nafion polymer solution that adopts the present invention to add NaOH prepares are as follows: (need to prove, anode electrocatalyst and electrocatalyst for cathode that the present invention adopts are known technology, and anode electrocatalyst can be Pt/C, Pt
3Sn/C, PtRu/C, Pt
3W/C or PtRu are black; Electrocatalyst for cathode can be Pt
3Cr/C, Pt
3Fe/C, Pt
3Co/C, Pt/C, Pt
3Pd/C or Pt are black.For these known technologies, do not enumerate one by one in an embodiment for simplicity's sake.)
(1) anode catalyst layer preparation: take by weighing 400mg 5%Nafion solution in measuring cup, add 1900mg water and 300mg 0.5M NaOH solution respectively, ultrasonic mixing, add 96mgPtRu black (Johnson Matthey company) then, mix and obtain catalyst slurry, use nozzle to be sprayed on the sodium typeization
One side of 115 films (DuPont company), catalyst loading is 3.2mg/cm
2
(2) cathode catalysis layer preparation: take by weighing 160mg 5%Nafion solution in measuring cup, add 1000mg deionized water and 160mg 0.5M NaOH solution respectively, mix the back and add 50mg Pt black (Johnson Matthey company), ultrasonic concussion 15 minutes obtains catalyst slurry.Then catalyst slurry is sprayed on the opposite side of Nafion film, catalyst loading is 2.3mg/cm
2Obtain being covered with the film (CCM) of catalyst.
(3) diffusion layer preparation: use two SGL GDL-20-AA carbon papers, after repeatedly flooding with the 10%PTFE emulsion respectively, in muffle furnace,, make anode and cathode support layer respectively 340 ℃ of following sintering 40 minutes to 1 hour.Wherein PTFE content is 10% in the anode support, and PTFE content is 30% in the cathode support layer.
Get a certain amount of carbon dust, add adequate amount of ethanol, behind the sonic oscillation, add an amount of Nafion (5%
Emulsion, EW1100), again sonic oscillation and stir 5 minutes after, be distributed to and obtain anode diffusion layer on the anode support.The carbon dust carrying capacity is 5.0mgcm
-2, Nafion content is 10%.
Get a certain amount of carbon dust, add an amount of ethanol, after sonic oscillation disperses, add after an amount of 10%PTFE emulsion mixes, be distributed on the cathode support layer and obtain cathode diffusion layer.The carbon dust carrying capacity is 3.0mgcm
-2, PTFE content is 20%.Be placed in the muffle furnace 340 ℃ of following sintering 40 minutes, cooling, standby.
(4) Hydrogen processing: with the CCM that makes 0.5M H
2SO
4Handle twice, each 60 minutes at 80 ℃.And then handle twice, each 60 minutes with 80 ℃ of deionized waters.
The membrane electrode performance characterization:
CCM anode and cathode Catalytic Layer both sides with the anode and cathode diffusion layer places above-mentioned steps to make respectively obtain MEA1, assembled battery.
The sign of cathod catalyst utilance: after the MEA1 that makes was assembled into battery, anode was as reference with to electrode, and negative electrode carries out cyclic voltammetry scan as work electrode between 0～1.2V, and sweep speed is 20mV/s.Calculate the utilance of catalyst according to the BET surface area of oxidation peak area and catalyst.Experimental result sees Table 1, and the cathod catalyst utilance can reach 65% among the MEA1.
The performance curve of membrane electrode MEA1 in the time of 75 ℃ as shown in Figure 2, operating condition: battery temperature is 75 ℃; 1mol/L methanol aqueous solution 1ml/min sample introduction; 0.2MPa oxygen, flow velocity are 3.5ml/s.As shown in Figure 2, the battery that membrane electrode MEA1 of the present invention is assembled into, maximum power output density can reach 200mW/cm
2
Embodiment 3
Hydrogen Nafion polymer manufacture electrode and MEA performance
For the ease of effect more of the present invention, get sodium type Nafion 115 films, prepare the anode catalyst slurries according to the method for embodiment 2, be painted on the film.Do not add 0.5M NaOH solution in the cathod catalyst slurries.All the other preparation methods are identical with embodiment 2 with catalyst loading.
The membrane electrode of this method preparation is designated as MEA2.
The cathod catalyst utilance of MEA2 is 58%, sees Table 1.75 ℃ of performances are seen Fig. 2, and its maximum power output density can reach 160mW/cm
2
The cathod catalyst utilance of contrast MEA1 and MEA2 uses the electrode catalyst utilance and the battery performance of the inventive method preparation all to be able to obvious raising as can be seen.
Adopting pure water mixed solvent configuration catalyst slurry to prepare electrode, to adopt water with embodiment 2 be the performance comparison that solvent configuration catalyst slurry prepares electrode
Method for preparing membrane electrode is with embodiment 2 in the present embodiment, and just the anode catalyst slurries adopt pure water mixed solvent.
The preparation of anode catalyst slurries: take by weighing 400mg 5%Nafion solution in measuring cup, add 960mg deionized water and 300mg 0.5M NaOH solution respectively, ultrasonic concussion mixes the back and adds black (the Johnson Matthey company) catalyst of 96mg PtRu, add the 960mg absolute ethyl alcohol at last, mix and obtain catalyst slurry.
The membrane electrode of this method preparation is designated as MEA3.The anodic polarization curves of MEA1 and MEA3 is seen Fig. 3.
Embodiment 5
Adopting the PTFE film is the substrate preparation Catalytic Layer
(1) anode catalyst layer preparation: 500mg 5%Nafion solution, add deionized water 3000mg, add 300mg 0.5M Na again
2SO
4Solution, ultrasonic concussion mixes, and adds 100mgPt (40%) Ru (20%)/C (Johnson Matthey) then, mixes and obtains catalyst slurry, and it is sprayed in the substrate of PTFE film, and catalyst loading is 4.5mg/cm
2
(2) cathode catalysis layer preparation: take by weighing 250mg 5% Nafion solution, add deionized water 1000mg, add 250mg 0.5M NaOH solution again, mix the back and add 50mg Pt/C (60%) (Johnson Matthey), ultrasonic concussion 15 minutes, obtain catalyst slurry, it is sprayed in the substrate of PTFE film.Catalyst loading is 3.0mg/cm
2
(3) MEA preparation: cutting effective area respectively is 2 * 2cm
2The PTFE film that is covered with negative electrode and anode catalyst layer, place Na type Nafion 115 film both sides, 190 ℃, preheating 2 minutes, pressing is 3 minutes under the 40MPa, takes out cooling, remove the PTFE film, after then this being had the Nafion film Hydrogen processing of Catalytic Layer, the anode and cathode diffusion layer is placed its both sides, obtain MEA4.
The performance curve of membrane electrode MEA4 in the time of 75 ℃ as shown in Figure 4, operating condition: battery temperature is 75 ℃; 1mol/L methanol aqueous solution 1ml/min charging; 0.2MPa oxygen, flow velocity are 3.5ml/s.The utilance of cathod catalyst sees Table 1.
Embodiment 6
Adopting diffusion layer is the substrate preparation Catalytic Layer
Anode catalyst slurry preparation method adopts nozzle to spray to (E019/DS/V2, E-TEK company) on the diffusion layer with embodiment 5.All the other preparation methods are with embodiment 5.Obtain MEA5.The performance curve of membrane electrode MEA4 in the time of 75 ℃ as shown in Figure 4, operating condition: battery temperature is 75 ℃; 1mol/L methanol aqueous solution 1ml/min sample introduction; 0.2MPa oxygen, flow velocity are 3.5ml/s.As seen from Figure 4, as the E019/DS/V2 that adopts commodity during as anode diffusion layer, catalyst slurry directly being prepared on the diffusion layer and catalyst slurry is prepared into changes the MEA performance that compacting obtains fully and is more or less the same on the PTFE film.
Cathod catalyst utilance under 75 ℃ of conditions of membrane electrode among table 1. embodiment
Claims (7)
1, the method for making of a kind of proton exchange membrane fuel cell electrode and membrane electrode, step is as follows:
A) preparation catalyst slurry
The first step, the dispersion of polymer dielectric: polymer dielectric solution, deionized water and the first main group alkali metal hydroxide or its esters compound solution are mixed;
In second step, catalyst mixes with the polymer dielectric solution of dispersion: anode electrocatalyst is joined in the solution that is prepared by the first step, mix, obtain the anode catalyst slurries;
Electrocatalyst for cathode is joined in the solution that is prepared by the first step, mix, obtain the cathod catalyst slurries;
B) electrode of preparation fuel cell: catalyst slurry disperses/deposits to conductive substrates, leads on proton substrate or the non-conductive substrate film;
Its content of described polymer dielectric is the 5-50% of electrode dry weight;
The mole ratio of sulfonate group is 1 in the first main group alkali metal hydroxide or its esters compound and the polymer dielectric: 1-10: 1;
Wherein polymer dielectric is Nafion polymer or Flemion polymer.
2, according to the described method for making of claim 1, wherein, the alkali-metal hydroxide solution of first main group is NaOH, KOH, Na
2SO
4, K
2SO
4, NaCl or KCl solution.
3,, wherein, after second step of steps A, add monohydric alcohol or ethylene glycol organic solvent according to the described method for making of claim 1.
4, according to the described method for making of claim 1, wherein, monohydric alcohol is ethanol or isopropyl alcohol.
5, according to the described method for making of claim 1, wherein, substrate film is porous gas diffusion layer, proton exchange membrane, poly tetrafluoroethylene.
6, according to the described method for making of claim 1, wherein, anode electrocatalyst is: Pt/C, Pt
3Sn/C, PtRu/C, Pt
3W/C or PtRu are black.
7, according to the described method for making of claim 1, wherein, electrocatalyst for cathode is: Pt
3Cr/C, Pt
3Fe/C, Pt
3Co/C, Pt/C, Pt
3Pd/C or Pt are black.
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| CN100454636C (en) * | 2007-03-29 | 2009-01-21 | 武汉理工大学 | Making method for core component of water-reservation proton exchange film fuel battery |
| CN101237060B (en) * | 2008-02-28 | 2011-05-11 | 武汉理工大学 | Fuel battery catalyzer layer and film pole based on multi-hold base and its making method |
| CN108461786A (en) * | 2016-12-10 | 2018-08-28 | 中国科学院大连化学物理研究所 | A kind of preparation method and fuel cell of fuel cell membrane electrode |
| CN109390592B (en) * | 2017-08-04 | 2021-12-31 | 上海汽车集团股份有限公司 | Membrane electrode and preparation method thereof |
| CN110323460B (en) * | 2019-07-03 | 2021-01-19 | 深圳市南科燃料电池有限公司 | Catalyst slurry, preparation method and fuel cell |
| CN112980247A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | High-stability ink-jet printing ink for fuel cell and preparation and application thereof |
| CN112271301B (en) * | 2020-10-16 | 2021-11-23 | 山东汉德自动化控制设备有限公司 | Method for preparing fuel cell membrane electrode by inorganic in-situ adhesion |
| CN114540854A (en) * | 2022-03-18 | 2022-05-27 | 中国科学院长春应用化学研究所 | SPEWE membrane electrode and preparation method thereof |
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| US6344428B1 (en) * | 1998-05-04 | 2002-02-05 | Samsung Electronics Co., Ltd. | Method of forming catalyst layer for fuel cell |
| CN1612381A (en) * | 2003-10-27 | 2005-05-04 | 中国科学院大连化学物理研究所 | Membrane electrode structure for proton exchange membrane fuel cell and its preparing method |
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| US6344428B1 (en) * | 1998-05-04 | 2002-02-05 | Samsung Electronics Co., Ltd. | Method of forming catalyst layer for fuel cell |
| CN1612381A (en) * | 2003-10-27 | 2005-05-04 | 中国科学院大连化学物理研究所 | Membrane electrode structure for proton exchange membrane fuel cell and its preparing method |
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