CN1315221C - Full cross-linked proton exchange film fuel cell chip and preparing process - Google Patents

Full cross-linked proton exchange film fuel cell chip and preparing process Download PDF

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CN1315221C
CN1315221C CNB2005100187413A CN200510018741A CN1315221C CN 1315221 C CN1315221 C CN 1315221C CN B2005100187413 A CNB2005100187413 A CN B2005100187413A CN 200510018741 A CN200510018741 A CN 200510018741A CN 1315221 C CN1315221 C CN 1315221C
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proton exchange
film
fuel cell
catalyst
cell chip
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CN1688053A (en
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木士春
赵培
陈磊
潘牧
袁润章
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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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

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Abstract

The present invention relates to a chip for proton exchange membrane fuel batteries and a method for preparing the chip. A connecting layer of the chip for fuel batteries is fully crosslinked with proton exchange resin in a proton exchange membrane and a catalyst layer, so that the chip for fuel batteries has favorable binding strength. The chip for fuel batteries is prepared through a transfer method, and the method for preparing the chip comprises the steps that the surfaces of transfer media are coated with catalyst layers, the surfaces of the catalyst layers are further coated with proton exchange resin solution to prepare the connecting layers, and the proton exchange membrane is put between two sheets of transfer media coated with the proton exchange resin. The chip for fuel batteries is obtained through hot-pressing.

Description

A kind of full cross-linked proton exchange film fuel cell chip and preparation method
Technical field
The present invention relates to a kind of proton exchange film fuel cell chip is core components of PEMFC CCM (CatalystCoated Membrane) and preparation method, particularly through full cross-linked fuel cell chip and preparation method.
Background technology
Fuel cell is pem fuel (Proton Exchange Membrane Fuel Cell particularly, PEMFC) battery has very wide application prospect because of noiselessness, pollution-free, advantage such as working temperature is low, specific power density is big in industries such as mobile communication equipment, portable electronics, national defence critical equipment, mechanical transports.But the performance of fuel cell chip CCM (catalyst coatedmembrane) and price are one of business-like significant obstacle of restriction fuel cell always.
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, can be described as 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 catalyst and the membrane module that the catalyst layer of its both sides constitutes.Because the whole electrochemical reaction of fuel cell is all finished on CCM, so CCM can be described as the most crucial parts of fuel cell, act on suitable with computer chip, so fuel cell chip that is otherwise known as.Compare with gaseous diffusion layer assembly (Catalyst Coated GDL) with traditional catalyst, CCM has comparatively outstanding advantage:
1) functionalization that helps fuel cell module is distinguished.The notion of catalyst and gaseous 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 membrane electrode electric current.And in the catalyst/gas 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, and 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, helps 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.But CCM wants commercialization, also needs further to improve its endurance quality.The main path that improves the CCM endurance quality at present has: 1) improve the endurance quality of catalyst layer, comprise the endurance quality of catalyst etc.; 2) endurance quality of raising proton exchange membrane comprises and improves mechanical strength, dimensional stability and anti-degradation capability etc.; 3) improve the interfacial structure of catalyst layer and proton exchange membrane, improve the bond strength of catalyst layer and proton exchange membrane, prevent battery, the performance of reduction battery thereby catalyst comes off from the both sides of film because of after working over a long time.Wherein the 3rd approach is the basis of realizing preceding two approach, also is the key that realizes improving the fuel cell durability energy.Therefore, be necessary to improve the bond strength of catalyst layer and proton exchange membrane, but the research of this respect also rarely has report at present.
Summary of the invention
The invention provides a kind of proton exchange film fuel cell chip and preparation method thereof, particularly full cross-linked fuel cell chip and preparation method between catalyst layer and the proton exchange membrane.
A kind of proton exchange film fuel cell chip of the present invention is to pass through the full cross-linked fuel cell chip of intermediate connecting layer between catalyst layer and the proton exchange membrane, and catalyst layer is made up of catalyst and proton exchange resins.
Catalyst layer of the present invention mainly comprises catalyst and proton exchange resins.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.Wherein, the Pt alloy 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 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.
Proton exchange membrane of the present invention is the Nafion of perfluoro sulfonic acid membrane class Film, Dow Film, Flemion Film, Aciplex Film, partially fluorinated proton exchange membrane, BAM3G film as Ballard company, the proton exchange membrane of nonfluorinated, sulfonated phenylethylene and butylene vinyl and styrene triblock copolymer film (SEBS) as the exploitation of Dais company, the blend film of inorganic acid and resin as phosphate-doped PBI film, is the Gore-select of substrate with the polytetrafluoroethylporous porous membrane TMComposite membrane.
The preparation method of fuel cell chip of the present invention, its preparation process is followed successively by:
1) catalyst, proton exchange resins are mixed by 10: 2～5: 50～500 mass ratio is full and uniform with solvent, make catalyst slurry, described solvent is water or organic solvent alcohol, ether, ester or ketone, wherein alcohol is methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycerol or 1-methoxyl group 2-propyl alcohol, ether is ether, benzinum, ester is an ethyl acetate, and ketone is acetone;
2) adopt spraying process, rubbing method or silk screen print method that the catalyst slurry that step 1 makes is coated to PolytetrafluoroethylFilm Film, and intensive drying, the thickness of catalyst layer is 1～5 μ m;
3) adopt spraying process, rubbing method, silk screen print method or infusion process that proton exchange resins solution is coated to catalyst layer surface on the polytetrafluoroethylene film that step 2 makes, make articulamentum, articulamentum thickness is 0.1～2 μ m;
4) proton exchange membrane is placed in the middle of two coated film that step 2 makes, wherein proton exchange membrane contacts with the articulamentum of coated film, form three-in-one assembly, after hot pressing, articulamentum is transferred to the proton exchange membrane both sides, and it is full cross-linked with the proton exchange resins generation in proton exchange membrane and the catalyst layer, peel off polytetrafluoroethylene film, promptly make proton exchange film fuel cell chip, its hot pressing temperature is 80～135 ℃, pressure is 0.2～5MPa, and hot pressing time is 1～5min.
The present invention compares with background technology, the fuel cell chip of preparation has articulamentum, and the proton exchange resins in articulamentum and proton exchange membrane and the catalyst layer is full cross-linked under hot pressing function, so the adhesion between catalyst layer and the proton exchange membrane is strengthened.
Description of drawings
Fig. 1 is the composition and the preparation process schematic diagram of fuel cell chip of the present invention.
The number in the figure implication:
1-polytetrafluoroethylene film layer, 2-catalyst layer, 3-proton exchange resins solution, 4-proton exchange membrane
The A-polytetrafluoroethylene film, B-is at PolytetrafluoroethylFilm Film coating catalyst layer, C-is at catalyst layer surface coating proton exchange resins solution, the preparation articulamentum, D-places between two polytetrafluoroethylene films that are coated with proton exchange resins solution proton exchange membrane and hot pressing, E-throws off polytetrafluoroethylene film, makes fuel cell chip of the present invention.
Fig. 2 is that fuel cell chip catalyst layer and proton exchange membrane bond strength compare.
Fig. 3 is the polarization curve of monocell.
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 P catalyst (production of U.S. Johnson Matthey company): Nafion  portions of resin 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 the polytetrafluoroethylene (PTFE) film surface, dry 1h, form catalyst layer, the PTFE film is the non-directional film, thickness 50～150 μ m.Adopt spraying process with Nafion Solution (the Nafion resin content is 1wt%, and U.S. Dupont company produces) sprays to catalyst layer surface equably, coating is carried out dried therebetween, makes the coated film that there is articulamentum on the surface;
Nafion  211 films are placed between the articulamentum of two coated film, it is carried out hot-pressing processing, hot pressing temperature is 130 ℃, and the time is 2 minutes, and pressure is 0.6MPa, divests polytetrafluoroethylene film, makes CCM.
The CCM accelerated test: place 30% pure water to soak and heating CCM, heating-up temperature is 100 ℃, and be 1000h heating time.The analysis result of comprehensive perusal and sem photograph (SEM), the expulsion rate of calculating proton exchange membrane surface catalyst layer, computing formula is: [(Aa-Av)/Aa] * 100%.Wherein, Aa is the active area of fuel cell chip, the white space area of the catalyst-free layer that Av forms on film for coming off because of catalyst.The expulsion rate of prepared CCM is illustrated among Fig. 2.
Monocell assembling and the performance test of CCM: diffusion layer adopts the alkali 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 100%, and humidification damp-warm syndrome degree is 70 ℃, Pt carrying capacity 0.3mg/cm 2(anode 0.1mg/cm 2, negative electrode 0.2mg/cm 2).The polarization curve of battery is illustrated among Fig. 3 during 70 ℃ of its battery temperatures
Embodiment 2
The method of testing of the preparation of catalyst slurry, catalyst slurry coating method, monocell is identical with embodiment 1, difference is, preparation method's difference of articulamentum: its preparation method is that the catalyst layer surface that polytetrafluoroethylene film one side applies is immersed in Nafion Solution (the Nafion resin content is 1wt%) floods after the drying 2 times again, makes articulamentum.The expulsion rate of prepared CCM is illustrated among Fig. 2, and the polarization curve of battery is illustrated among Fig. 3 during 70 ℃ of its battery temperatures.
Embodiment 3
The method of testing of the preparation of catalyst slurry, catalyst slurry coating method, monocell is identical with embodiment 1, and difference is, preparation method's difference of articulamentum: adopt rubbing method with Nafion Solution (the Nafion resin content is 5wt%) is coated to catalyst layer surface, floods after the drying 1 time again, makes articulamentum.The expulsion rate of prepared CCM is illustrated among Fig. 2, and the polarization curve of battery is illustrated among Fig. 3 during 70 ℃ of its battery temperatures.
Comparing embodiment 1
The method of testing of the preparation of catalyst slurry, catalyst slurry coating method, monocell is identical with embodiment 1, and difference is that the CCM of preparation does not have articulamentum.The polarization curve of battery is illustrated among Fig. 3 during 70 ℃ of its battery temperatures.
Be not difficult to find out that no matter the CCM of the present invention's preparation is at the CCM that all is better than no articulamentum aspect bond strength, the battery performance.

Claims (4)

1, a kind of proton exchange film fuel cell chip is characterized in that: this chip is to pass through the full cross-linked fuel cell chip of proton exchange resins articulamentum between catalyst layer and the proton exchange membrane, and catalyst layer is made up of catalyst and proton exchange resins.
2, fuel cell chip according to claim 1, it is characterized in that, 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, and described proton exchange film resin is the Nafion that du Pont company produces Resin, the Kraton G1650 resin that Dias company produces, or sulfonation thermal stability polymer, Flemion proton conductor polymer with proton exchange function.
3, fuel cell chip according to claim 1 is characterized in that proton exchange membrane is the Nafion of perfluoro sulfonic acid membrane class Film, Dow Film, Flemion Film and Aciplex Film, the partially fluorinated film of BAM3G that Ballard company produces, sulfonated phenylethylene and the butylene vinyl and the styrene triblock copolymer film of the exploitation of Dais company, the PBI film of phosphoric acid and resin alloy is the Gore-select of substrate with the polytetrafluoroethylporous porous membrane TMComposite membrane.
4, the preparation method of the described fuel cell chip of claim 1 is characterized in that preparation process is followed successively by:
1) catalyst, proton exchange resins are mixed by 10: 2～5: 50～500 mass ratio is full and uniform with solvent, make catalyst slurry, described solvent is water or organic solvent alcohol, ether, ester or ketone, wherein alcohol is methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycerol or 1-methoxyl group 2-propyl alcohol, ether is ether, benzinum, ester is an ethyl acetate, and ketone is acetone;
2) adopt spraying process, rubbing method or silk screen print method that the catalyst slurry that step 1) makes is coated to PolytetrafluoroethylFilm Film, and intensive drying, the thickness of catalyst layer is 1～5 μ m;
3) adopt spraying process, rubbing method, silk screen print method or infusion process that proton exchange resins solution is coated to step 2) catalyst layer surface on the polytetrafluoroethylene film that makes, make articulamentum, articulamentum thickness is 0.1～2 μ m;
4) proton exchange membrane is placed in the middle of two coated film that step 3) makes, wherein proton exchange membrane contacts with the articulamentum of coated film, form three-in-one assembly, after hot pressing, articulamentum is transferred to the proton exchange membrane both sides, and the while is full cross-linked with the proton exchange resins generation in proton exchange membrane and the catalyst layer, divest polytetrafluoroethylene film, promptly make proton exchange film fuel cell chip, hot pressing temperature is 80～135 ℃, pressure is 0.2～5MPa, and hot pressing time is 1～5min.
CNB2005100187413A 2005-05-19 2005-05-19 Full cross-linked proton exchange film fuel cell chip and preparing process Expired - Fee Related CN1315221C (en)

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KR100874112B1 (en) * 2007-06-25 2008-12-15 한화석유화학 주식회사 Process for preparing of a catalyst solution for fuel cell and a membrane electrode assembly using the same
CN101702436B (en) * 2009-10-26 2012-06-27 新源动力股份有限公司 Sizing agent for proton exchange membrane fuel cell electrodes and preparation method thereof
CN108011120B (en) * 2017-11-29 2021-04-23 中国科学技术大学 Preparation method of membrane electrode
CN108011109B (en) * 2017-11-29 2021-04-23 中国科学技术大学 Preparation method of membrane electrode and fuel cell
CN110970644A (en) * 2019-12-26 2020-04-07 先进储能材料国家工程研究中心有限责任公司 Proton exchange membrane fuel cell and preparation method thereof

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CN1560949A (en) * 2004-02-20 2005-01-05 �人����ѧ Catalyst coated membrane fuel cell by indirect method ultrathin core assembly for synthetising
CN1610145A (en) * 2004-11-15 2005-04-27 武汉理工大学 Method for producing multi-layer nano composite proton exchange membrane with self-humidifying function

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1560949A (en) * 2004-02-20 2005-01-05 �人����ѧ Catalyst coated membrane fuel cell by indirect method ultrathin core assembly for synthetising
CN1610145A (en) * 2004-11-15 2005-04-27 武汉理工大学 Method for producing multi-layer nano composite proton exchange membrane with self-humidifying function

Non-Patent Citations (1)

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Title
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