CN103594722B - Proton Exchange Membrane Fuel Cells - Google Patents
Proton Exchange Membrane Fuel Cells Download PDFInfo
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- CN103594722B CN103594722B CN201210292473.4A CN201210292473A CN103594722B CN 103594722 B CN103594722 B CN 103594722B CN 201210292473 A CN201210292473 A CN 201210292473A CN 103594722 B CN103594722 B CN 103594722B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
- H01M4/861—Porous electrodes with a gradient in the porosity
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
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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
The invention provides a proton exchanging film fuel battery (PEMFC).In the cell, anode be specific surface area be 80～130m2The mesoporous WO of/g3/ C composite, does not use noble metal (such as Pt, Au, Ph, Pd, Ru etc.) catalyst；Negative electrode be specific surface area be 100～140m2The mesoporous Pt/WC composite of/g, substitutes conventional activated carbon as catalyst carrier material using mesoporous WC.The Proton Exchange Membrane Fuel Cells of the present invention not only shows high electric current output and power density, also there is good CO tolerance catalysts performance and good service life, its power density can reach normal cell under the operating temperature of 80 DEG C, and (anode is 20wt%Pt/C, negative electrode is 40wt%Pt/C) 82%, and after using 120 hours continuously, its output voltage still maintains original 72%.The anode of such PEMFC of the present invention does not use noble metal, is not only substantially reduced the cost of battery, it is thus also avoided that the intoxicating phenomenon of positive C O, also eliminates oxidizable, the problem of corrosion of cathode activity carbon carrier simultaneously.
Description
Technical field
The present invention relates to a kind of new proton exchange film fuel battery (PEMFC), the anode in described battery is the composite materials of the meso-hole structure of non-noble-metal-supported, and negative electrode is the composite materials of the meso-hole structure of non-carbon support.
Technical background
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of with hydrogen or hydrogen-containing gas as fuel, the TRT as oxidant with oxygen or air, there is operating temperature low (< 100 DEG C), start fast, capacity usage ratio advantages of higher, be suitable for household electrical source, electric automobile, split the application of the aspect such as power station and portable type electronic product.As the electrode catalyst agent material of one of battery critical material be related to PEMFC can the of paramount importance material of popularization and application.
The most domestic and international reported PEMFC anode catalyst material, being substantially with platinum metal (such as Pt, Au, Ph, Pd, Ru etc.) is main noble metal catalyst, and such noble metal catalyst has high catalysis activity to the electrochemical oxidation of hydrogen.But, precious metals pt catalyst when the reformer hydrogen containing CO is fuel, easily CO absorption molecule, occur the CO of Pt catalyst " to be poisoned " phenomenon, thus cause the inactivation of Pt catalyst.In order to avoid the CO of Pt catalyst " is poisoned " phenomenon, PtRu binary, PtRuW or PtRuMo ternary alloy catalyst are developed again, and wherein PtRu bianry alloy catalyst is maximally efficient anti-CO anode catalyst.But, PtRu is noble metal, expensive, significantly hinders the large-scale commercial applications of PEMFC.Develop highly active novel non-noble metal anti-CO anode catalyst, while keeping high catalytic efficiency, there is good CO tolerance catalysts performance, one of focus in always PEMFC application.
Negative electrode for PEMFC, conventional catalyst is activated carbon loaded Pt catalyst (Pt/C) material, but, an activity carbon carrier material weak point in PEMFC negative electrode is applied is exactly, easily there is the oxidation of carbon, corrosion when being chronically in cathode oxidation atmosphere use in it, peels off from electrode diffusion layer, loses the effect of conduction afflux, affect the output of battery current, thus cause the reduction of battery performance.Develop one of a kind of cathode catalyst support material research emphasis having become PEMFC cathod catalyst with antioxidation and antiacid corrosion.
Mesoporous material has high specific surface area, the pore passage structure of rule and controllable bore diameter size, is preferable catalyst material in catalytic field.Tungsten oxide has special chemical property, the WO of meso-hole structure3, its electro-chemical activity can improve further.Our seminar is with the mesoporous WO of Template synthesis3Material list reveals high electrochemical catalysis performance (J.Mater.Chem., 2008,18,575 3580).Tungsten carbide is a kind of non-oxidizability and the strong carbide material of antiacid corrosivity, and has good electric conductivity.In the present invention, we have proposed a kind of anode base metal for PEMFC and load the electrode catalyst agent material of the meso-hole structure of negative electrode non-carbon support simultaneously, the most mesoporous WO of such catalyst material middle-jiao yang, function of the spleen and stomach3/ C composite materials, negative electrode is mesoporous Pt/WC composite materials, and anode does not use noble metal, negative electrode does not use activity carbon carrier, is possible not only to be substantially reduced the cost of battery, it is also possible to avoid the CO intoxicating phenomenon of anode, meanwhile, it also avoid oxidizable, the etching problem of cathode activity carbon.This at home and abroad yet there are no relevant report.
Summary of the invention
In order to solve problems of the prior art, the present invention provides a proton exchanging film fuel battery, described battery to include the mesoporous WO of the base metal load as anode3/ C composite, PEM and the mesoporous Pt/WC composite of the non-carbon support as negative electrode.
Wherein, described mesoporous WO3/ C composite and mesoporous Pt/WC composite preferably have the composite mesoporous thing material of crystallization hole wall.
In one embodiment of the present invention, the mesoporous WO of described base metal load3The specific surface area of/C composite is 80～130m2/g.The specific surface area of the mesoporous Pt/WC composite of described non-carbon support is 100～140m2/g。
In the present invention, described anode is with hydrogen or hydrogen-containing gas as fuel, and described negative electrode is with oxygen or air as oxidant.Described battery applications reacts field in electrochemical catalysis.
On the other hand, the present invention also provides for the mesoporous WO of a kind of base metal load3/ C anode composite.Wherein, the mesoporous WO of described base metal load3/ C anode composite specific surface area is 80～130m2/g。
Another aspect, the present invention provides the mesoporous Pt/WC cathode composite of a kind of non-carbon support.Wherein, the specific surface area of the mesoporous Pt/WC cathode composite of described non-carbon support is 100～140m2/g。
Specifically, it is an object of the invention to provide the PEMFC electrode catalyst agent material of a kind of anode base metal load negative electrode non-carbon support simultaneously.Anode in such catalyst material is the mesoporous WO with special chemical property3/ C composite, negative electrode is the Pt catalyst material of the mesoporous WC load with strong anti-oxidation and antiacid corrosion.In the Proton Exchange Membrane Fuel Cells of the present invention, anode does not use noble metal, not only reduces the cost of battery, it is also possible to avoid the CO of anode to be poisoned；Meanwhile, the application of negative electrode non-carbon support can avoid the oxidation of carrier material, etching problem.
In the present invention, the preparation scheme of the anode base metal of the meso-hole structure PEMFC electrode catalyst agent material of negative electrode non-carbon simultaneously is as follows:
(1) according to document (" chemical communication " (Chem.Commun.), 2003,35,2136；" science " (Science), 1998,279,548-552.) prepare or the most directly buy mesopore silicon oxide mould material (KIT-6 of three-dimensional cubic duct structure), do not remove surfactant P123(polyoxypropylene polyoxyethylene-polyoxypropylene), directly using it as preparing mesoporous WO3The hard template of/C composite；
(2) the mesoporous KIT-6 mould material 0.2-1.0g taking above-mentioned preparation is placed in hermetic container, is dissolved in 5-10ml dehydrated alcohol by 0.4g-3.0g phosphotungstic acid simultaneously, then by the method for vacuum pouring, the ethanol solution of tungsten salt is poured into mesoporous SiO2Duct in, continue evacuation within 10-50 minute, make ethanol volatilize, tungsten salt predecessor (precursor) is poured into mesoporous SiO completely2Duct in；
(3) by the mesoporous SiO being mounted with tungsten salt of above-mentioned preparation2After complex is dried in 40-100 DEG C of baking oven, it is placed in N2Carrying out heat treatment in protective atmosphere, 350-500 DEG C processes 2 hours, makes tungsten salt be decomposed to form the sexavalence tungsten oxide of correspondence, meanwhile, the surfactant P containing carbochain123Carry out in-situ carburization in an inert atmosphere, thus obtain carbon uniform load in the WO in duct3/CSiO2Complex；
(4) by the mesoporous SiO being mounted with tungsten salt of preparation in step (2)2Complex, a part is placed in H2/Ar(H2: Ar=7:93, volume ratio) atmosphere furnace carries out carbonization, it is raised to 650 DEG C with the heating rate of 10 DEG C/min, and this temperature 3-6 hour, is raised to 750 DEG C with the heating rate of 3 DEG C/min afterwards, and this temperature 3-6 hour, it is thus achieved that mesoporous WCSiO2Complex；
(5), after gained powder body in step (3) being removed silica template with 2M (mol/L) HF aqueous solution, i.e. can get the mesoporous WO of crystallization of pore wall3/ C composite；
(6), after gained powder body in step (4) being removed silica template with 2MHF aqueous solution, the mesoporous WC material of crystallization of pore wall is i.e. obtained；
(7) take mesoporous WC powder body prepared in 0.3g step (6), be distributed in 15ml deionized water, and be the H of 9.4mg/ml by Pt content2PtCl6Aqueous solution is added drop-wise in the suspension of mesoporous WC, continuously stirred 6 hours, then by the NaHB of 0.5M4Aqueous solution is slowly added dropwise in above-mentioned mixed solution, continuously stirred 12 hours；
(8) suspension in step (7) is centrifuged, washs and dries, i.e. can get the Pt/WC composite of meso-hole structure.
The mesoporous WO prepared according to process above flow process3The specific surface area of/C composite anode material is 80-130m2/ g, crystallization of pore wall.The specific surface area of mesoporous Pt/WC complex cathodes material is 100-140m2/ g, crystallization of pore wall.
The test of monocell:
In the Proton Exchange Membrane Fuel Cells of the present invention, anode with 99.99% pure H2For fuel, flow is 100sccm, and negative electrode is with pure O2For oxidant, flow is 100sccm.During CO resistance performance test, anode is (1%CO+99%H with the gaseous mixture containing 1%CO as fuel2), flow is 100sccm, and negative electrode is with pure O2For oxidant, flow is 100sccm.As a comparison, the normal cell electrode catalyst bought is anode 20wt%Pt/C-XC-72R, negative electrode is 40wt%Pt/C-XC-72R, E-Teck company of the U.S. produce.
Advantages of the present invention is as follows:
(1) anode catalyst is the mesoporous WO of base metal load3/ C composite, not only has high hydrogen electro-oxidizing-catalyzing activity, also has good CO resistance performance, can also be substantially reduced the cost of battery simultaneously；
(2) negative electrode is the mesoporous Pt/WC composite of non-carbon support, effectively prevent oxidizable, the etching problem of activity carbon carrier, it is simple to the afflux output of electric current, improves the efficiency of battery；
(3) with the mesoporous WO of the present invention3/ C composite and mesoporous Pt/WC composite are respectively as the anode of PEMFC and negative electrode, the output power density of the Proton Exchange Membrane Fuel Cells prepared can reach the 83% of normal cell at 80 DEG C, and after working 120 hours continuously, its output voltage has remained in that original 72%.And, containing in the mixing hydrogen that volume fraction is 1%CO, show good CO tolerance catalysts performance.
Accompanying drawing explanation
Fig. 1: intermediary hole WO of the present invention3/ C composite anode materials is at 0.5MH2SO4Electrochemistry CV (electric current-electromotive force) curve in solution, wherein, scanning speed 0.05V/s, room temperature.
Fig. 2: intermediary hole 20wt%Pt/WC composite cathode material of the present invention is at 0.1MHClO4Dynamic RDE(rotating disk electrode (r.d.e) in solution) CV curve, wherein, and scanning speed 0.02V/s, room temperature.
In Fig. 3, A is with mesoporous WO3When/C composite and mesoporous Pt/WC composite are respectively PEMFC anode and cathod catalyst, the current-voltage figure of monocell；
The power density curve of output of corresponding monocell in B:A.
Fig. 4: the monocell of Different electrodes catalyst type is at the work voltage-time curve of 120 hours continuously.
In Fig. 5, A is that the present invention is with mesoporous WO3Monocell when/C composite and mesoporous Pt/WC composite are respectively PEMFC anode and cathod catalyst and normal cell, the current-voltage curve figure when with the mixing hydrogen containing CO for fuel；
The power density output curve diagram of corresponding monocell in B:A.
Detailed description of the invention
Further illustrate the present invention below by embodiment and comparative example, make technical staff clearly understand advantages of the present invention.It should be understood that content therein is used merely as explanation, and absolutely not protection scope of the present invention is construed as limiting.
Embodiment 1
According to technique scheme of the present invention and technological process, it is first according to document and prepares the KIT-6 mould material of three-dimensional cubic meso-hole structure, do not remove the surfactant P in duct123.Take phosphotungstic acid 0.4g to be uniformly dissolved in 5ml dehydrated alcohol, then by the duct of mesoporous for its vacuum pouring to 0.2g KIT-6 template, continue evacuation 30 minutes, make tungsten salt presoma fully be poured in the duct of template.Then the silica composite being loaded with tungsten salt is placed in 60 DEG C of baking ovens drying 30 minutes, obtained powder body is put in blanket of nitrogen stove, be raised to 500 DEG C with the speed in 2 DEG C/min and be incubated 2 hours.Gained powder body removes removing template through 2MHF solution, be then centrifuged for separate, wash and be dried just obtained target product.Prepared mesoporous WO3The specific surface area of/C composite is: 110m2/ g(table 1), its to the electro-oxidizing-catalyzing of hydrogen as shown in the electrochemistry CV curve in Fig. 1.
It is loaded with the silica composite of tungsten salt is placed in H it addition, take2/Ar(H2: Ar=7:93, volume ratio) atmosphere furnace carries out carbonization, it is raised to 650 DEG C with the heating rate of 10 DEG C/min, and this temperature 3 hours, is raised to 750 DEG C with the heating rate of 3 DEG C/min afterwards, and this temperature 3 hours, it is thus achieved that mesoporous WCSiO2Complex.Products therefrom removes removing template through 2MHF solution, is then peeled off, wash and be dried just obtained the mesoporous WC of target product.Take 0.3g mesoporous WC powder body, be distributed in 15ml deionized water, and be the H of 9.4mg/ml by Pt content2PtCl6Aqueous solution 8ml is added drop-wise in the suspension of mesoporous WC, continuously stirred 6 hours, then by the NaHB of 0.5M4Aqueous solution is slowly added dropwise in above-mentioned mixed solution, continuously stirred 12 hours.And this suspension is centrifuged, washs and dries, obtain the 20wt%Pt/WC composite of meso-hole structure.The specific surface area of prepared mesoporous 20wt%Pt/WC is: 128m2/ g(table 1), the electrochemical catalysis of oxygen is reduced as shown in dynamic rotary disk (RDE) the electrochemistry CV curve in Fig. 2 by it.
Embodiment 2
According to described in technological process (with embodiment 1), take phosphotungstic acid 1.2g to be uniformly dissolved in 10ml dehydrated alcohol, then vacuum pouring is in 0.5g mould material, then the silica composite being loaded with tungsten salt is placed in 100 DEG C of baking ovens drying 60 minutes, the powder body of gained is put in blanket of nitrogen stove by obtained powder body, being raised to 450 DEG C with the speed in 2 DEG C/min and be incubated 4 hours, other operations, with embodiment 1, prepare mesoporous WO3/ C composite.
The preparation of mesoporous WC material, with embodiment 1, takes 0.3g mesoporous WC powder body, is distributed in 15ml deionized water, and is the H of 9.4mg/ml by Pt content2PtCl6Aqueous solution 21ml is added drop-wise in the suspension of mesoporous WC, continuously stirred 6 hours, then by the NaHB of 0.5M4Aqueous solution is slowly added dropwise in above-mentioned mixed solution, continuously stirred 12 hours, and other operations, with embodiment 1, obtain the 40wt%Pt/WC composite of meso-hole structure.
The specific surface area of prepared mesoporous 40wt%Pt/WC is: 113m2/ g(table 1).The mesoporous WO of preparation3/ C and mesoporous 40wt%Pt/WC is respectively as the anode of battery and negative electrode, and monocell output power density under room temperature (25 DEG C) reaches as high as 16.2mW/cm2(Fig. 3 A and 3B), after this battery works 120 hours continuously, its cell voltage has remained in that original 72%(Fig. 4), and this battery with containing 1% the mixing H of CO2During for fuel, battery current and output power density do not have significant change, and its CO tolerance catalysts effect is substantially better than (Fig. 5) of normal cell.
Embodiment 3
According to described in technological process (with embodiment 1), take phosphotungstic acid 2.5g to be uniformly dissolved in 20ml dehydrated alcohol, then vacuum pouring is in 1.0g mould material, then the silica composite being loaded with tungsten salt is placed in 40 DEG C of baking ovens drying 60 minutes, the powder body of gained is put in blanket of nitrogen stove by obtained powder body, being raised to 400 DEG C with the speed in 2 DEG C/min and be incubated 6 hours, other operations, with embodiment 1, prepare mesoporous WO3/ C composite.
The preparation of mesoporous WC carrier material and 40wt%Pt/WC composite is with embodiment 1.Mesoporous WO with preparation3/ C and mesoporous 40wt%Pt/WC is respectively anode and the negative electrode of battery, and the height (Fig. 3 A) under monocell battery current under the operating temperature of 40 DEG C and 60 DEG C substantially relatively room temperature, the output power density best result of its correspondence is not 17.5 and 20.5mW/cm2(Fig. 3 B), when 80 DEG C, the output power density of this battery can reach 24.6mW/cm2, for the 82%(29.8mW/cm of normal cell under the conditions of same test2), as shown in Figure 3 B.
Comparative example 1
According to described in technological process (with embodiment 1), prepare mesoporous WO3/ C composite, and prepare mesoporous 40wt%Pt/WC according to embodiment 2.Then with mesoporous WO3/ C is as the anode catalyst of PEMFC, using 40wt%Pt/C-XC-72R (Pt/C-E in figure) as cathod catalyst, prepared monocell is after working 120 hours continuously, its cell voltage maintains original 61%(Fig. 4), in the case of relatively same anode, with mesoporous 40wt%Pt/WC for (72%) low during negative electrode.When 40wt%Pt/C-XC-72R being described as cathod catalyst, activity carbon carrier part is oxidized, causes the decline of battery performance.
Comparative example 2
According to described in technological process (with embodiment 2), prepare mesoporous 40wt%Pt/WC composite, then using it as the cathod catalyst of PEMFC, using 20wt%Pt/C-XC-72R as anode catalyst, prepared monocell is after working 120 hours continuously, its terminal battery voltage is 0.42V, hence it is evident that higher than same anode using 40wt%Pt/C-XC-72R as (0.37V) of cathod catalyst.When further illustrating 40wt%Pt/C-XC-72R as cathod catalyst, activity carbon carrier part is oxidized, and mesoporous WC carrier has excellent antioxidation and acidresistant property.
The pore structure parameter of composite mesoporous thing material prepared by table 1.
Claims (4)
1. a proton exchanging film fuel battery, described battery includes the mesoporous WO loaded as the base metal of anode3/ C composite, PEM and the mesoporous Pt/WC composite of the non-carbon support as negative electrode；
Wherein, the mesoporous WO of described base metal load3/ C composite is obtained by in-situ carburization so that carbon uniform load in mesoporous WO3In duct；
The mesoporous WO of described base metal load3The specific surface area of/C composite is 80～130m2/g；And
The specific surface area of the mesoporous Pt/WC composite of described non-carbon support is 100～140m2/g。
Proton Exchange Membrane Fuel Cells the most according to claim 1, it is characterised in that described mesoporous WO3/ C composite and mesoporous Pt/WC composite are the composite mesoporous thing materials with crystallization hole wall.
Proton Exchange Membrane Fuel Cells the most according to claim 1, it is characterised in that described anode is with hydrogen or hydrogen-containing gas as fuel, and described negative electrode is with oxygen or air as oxidant.
Proton Exchange Membrane Fuel Cells the most according to claim 1, it is characterised in that described battery applications reacts field in electrochemical catalysis.
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| CN1994560A (en) * | 2006-12-21 | 2007-07-11 | 浙江工业大学 | Pt-supported tungsten carbide catalyst and preparation method thereof |
| CN102500360A (en) * | 2011-11-15 | 2012-06-20 | 中国科学院上海硅酸盐研究所 | Method for preparing mesoporous tungsten oxide/carbon composite conductive materials |
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| CN1994560A (en) * | 2006-12-21 | 2007-07-11 | 浙江工业大学 | Pt-supported tungsten carbide catalyst and preparation method thereof |
| CN102500360A (en) * | 2011-11-15 | 2012-06-20 | 中国科学院上海硅酸盐研究所 | Method for preparing mesoporous tungsten oxide/carbon composite conductive materials |
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| Electrochemical catalytic activity for the hydrogen oxidation of mesoporous WO3 and WO3/C composites;Xiangzhi Cui等;《Journal of Materials Chemistry》;20080702;第18卷(第30期);第3575页摘要；第3576页右栏第2段、右栏倒数第2段 * |
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