CN100536211C - New type direct methanol fuel cell - Google Patents

New type direct methanol fuel cell Download PDF

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Publication number
CN100536211C
CN100536211C CNB2007100237888A CN200710023788A CN100536211C CN 100536211 C CN100536211 C CN 100536211C CN B2007100237888 A CNB2007100237888 A CN B2007100237888A CN 200710023788 A CN200710023788 A CN 200710023788A CN 100536211 C CN100536211 C CN 100536211C
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China
Prior art keywords
gel
external electrode
electrode
fuel cell
methanol fuel
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CNB2007100237888A
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Chinese (zh)
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CN101093891A (en
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鞠剑峰
黄明宇
倪红军
吴东辉
华平
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Nantong University
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Nantong University
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Inert Electrodes (AREA)

Abstract

Without use of proton exchange membrane, the disclosed fuel battery includes shell of battery. Through welding point, the shell of battery is connected to outer electrode inside the shell. An air chamber is setup between the shell and the outer electrode. Inner electrode is setup at inner side of the outer electrode. Chamber of gel mobile phase is setup between inner electrode and outer electrode. An air chamber is setup at inner side of the inner electrode. Using gel mobile phase of possessing higher capability of conducting protons and electrons to replace solution mobile phase of liquid phase electrolyte of vitriol and methanol popular used currently, the invention solves issue of methanol leakage radically so as to lower poisoning cathode and anode catalyst of direct methanol fuel battery (DMFB). The invention raises performance of fuel battery, lowers manufacturing cost, and promotes progress of industrialization of DMFB.

Description

Direct methanol fuel cell
Technical field:
The present invention relates to a kind of methanol fuel cell that connects.
Background technology:
Direct methanol fuel cell (Direct Methanol Fuel Cell, DMFC) have that less energy consumption, energy density height, methyl alcohol source are abundant, low price, simple, convenient, the low noise advantages of operation of system, be considered to following automobile power and the most promising chemical power source of other vehicles, cause people's extensive concern.Direct methanol fuel cell development at present faces two big key issues: the one, and the solid electrolyte film that extensively adopts in direct methanol fuel cell is the Nafion film that was designed for originally in the hydrogen-oxygen proton exchange membrane fuel cell, it costs an arm and a leg, and tangible methanol leakage (crossover) phenomenon is arranged, methyl alcohol directly penetrates the Nafion film and runs off, methanol fuel is lost in a large number, the DMFC power density descends, the negative electrode of methanol leakage arrival simultaneously reacts on negative electrode, causes the cathod catalyst poisoning and shortens battery life greatly; The 2nd, methyl alcohol is slower in the anode surface oxidation rate, produces carboxyl species such as the CO of strong adsorption at anode surface in the oxidizing process, poisons electrode, and electrode activity is reduced.
Research both at home and abroad, the direct methanol fuel cell of using are all used proton exchange membrane.Proton exchange membrane general rising in DMFC led proton, electronic action.
The research of proton exchange membrane is at present mostly studied as compound, the modification of the solid electrolyte membrane material of proton exchange membrane etc. to improve it and lead the proton ability and to reduce the seepage to methyl alcohol.Document [1] is with chlorosulfonic acid solution sulfonation and the following four kinds of monomer M eSt of hydrolysis, tBuSt, DVB, the BVPE polymerization forms the ETFE film of high chemical stability, than Nafion film to low 6 times of the seepage of methyl alcohol.Document [2] has prepared the sulfonated polyether sulfone proton exchange membrane, to the seepage of methyl alcohol than the low 5-200 of Nafion 117 films doubly.Though the resistance leakage performance to methyl alcohol improves greatly, but still do not solve the leakage problems of methyl alcohol fully.
Summary of the invention:
The object of the present invention is to provide a kind ofly can effectively solve the infiltration problem of methyl alcohol on proton exchange membrane, do not use proton exchange membrane, improve performance of direct methanol fuel cells, reduce the new type direct methanol fuel cell of manufacturing cost.
Technical solution of the present invention is:
A kind of new type direct methanol fuel cell, it is characterized in that: do not use proton exchange membrane, comprise battery case, external electrode is set in the battery case, and external electrode is connected by pad with battery case, and between external electrode and the battery case air chamber is set, in the external electrode inboard interior electrode is set, the gel chamber mutually of flowing is set between interior electrode and the external electrode, in interior electrode inboard air chamber is set, wherein gel flows and is made by the raw material of following weight item:
CH 3OH 5～60％
H 2SO 4 10～30％
H 2O 20～60％
Heteroacid 3～10%
Conducting polymer and/or metal dust 2～6%
Metallo-organic compound or slaine 5～30%.
Interior electrode successively by POROUS TITANIUM PLATE, anode catalyst, gel flow phase, cathod catalyst, diffusion layer, POROUS TITANIUM PLATE is compound forms; External electrode successively by POROUS TITANIUM PLATE, diffusion layer, cathod catalyst, gel flow phase, anode catalyst, POROUS TITANIUM PLATE is compound forms.
Metallo-organic compound is titanate ester, silicate class, and slaine is a sodium metasilicate.Heteroacid is perfluorinated sulfonic acid, phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid or phosphor tin acid.Conducting polymer is polyaniline or polypyrrole, and metal dust is Cu, Ag or Au powder.
The mobile phase time of preparation gel, with metallo-organic compound or slaine is presoma, and the methyl alcohol in flowing mutually is decentralized medium, adds sulfuric acid, water, form colloidal sol through hydrolysis, polycondensation reaction, and further mix heteroacid, polymer and/or metal dust are made the mobile phase of gel.
The present invention is to have the moving phase of sulfuric acid, methyl alcohol liquid phase streams of electrolyte solution that the higher GeI (gel) that leads proton, electronic capability flows and replaces present generally use mutually, can fundamentally solve the problem of methanol leakage, reduce it to the poisoning of cathode in direct methanol fuel cells and anode catalyst, can improve the performance of direct methanol fuel cell; Simultaneously have higher proton and the electronic capability led mutually, played the effect of proton exchange membrane, therefore because GeI flows, in novel DMFC, can not use proton exchange membrane, thereby the simplification battery structure reduces its cost greatly, can promote the commercialization of direct methanol fuel cell.Patent of the present invention proposes the mobile moving phase of generally using at present of sulfuric acid, methyl alcohol liquid phase streams of electrolyte solution that replaces mutually with GeI first, and do not use the new type direct methanol fuel cell of proton exchange membrane, can be used as the electrokinetic cell of mancarried device such as mobile phone, notebook computer, mobile phone and motorcycle, automobile etc., realize commercial application.Can both micro fuel cell and battery pack can be made according to the requirement of reality use, also large-scale electricity fuel cell can be made.According to the practical application needs, battery can be made into different shape.
Description of drawings:
The invention will be further described below in conjunction with drawings and Examples.
Fig. 1 is the configuration diagram of one embodiment of the invention.
Fig. 2 is the configuration diagram of external electrode.
Fig. 3 is the configuration diagram of interior electrode.
Embodiment:
Embodiment 1:
A kind of new type direct methanol fuel cell, comprise battery case 1, external electrode 3 is set in the battery case, external electrode 3 is connected by pad 2 with battery case 1, and between external electrode 3 and the battery case 1 air chamber 17 is set, electrode 4 in the external electrode inboard is provided with, and the gel chamber 18 mutually of flowing is set between interior electrode 4 and the external electrode 3, in interior electrode inboard air chamber 19 is set, wherein gel flows and is made by the raw material of following weight item:
CH 3OH 20％
H 2SO 4 30％
H 2O 20％
Heteroacid 3%
Conducting polymer and/or metal dust 5%
Metallo-organic compound or slaine 22%.
Metallo-organic compound is titanate ester (or silicate class), and slaine is a sodium metasilicate.Heteroacid is perfluorinated sulfonic acid (or phosphotungstic acid or phosphomolybdic acid or silico-tungstic acid or phosphor tin acid).Conducting polymer is polyaniline (or polypyrrole), and metal dust is Cu (or Ag or Au powder).
The mobile phase time of preparation gel, with metallo-organic compound or slaine is presoma, and the methyl alcohol in flowing mutually is decentralized medium, adds sulfuric acid, water, form colloidal sol through hydrolysis, polycondensation reaction, and further mix heteroacid, polymer and/or metal dust are made the mobile phase of gel.
Interior electrode is successively by 10 compound compositions of POROUS TITANIUM PLATE 5, anode catalyst 6, gel flow mutually 7, cathod catalyst 8, porous carbon fiber paper or carbon cloth are formed diffusion layer 9, POROUS TITANIUM PLATE; The diffusion layer 12 that external electrode is made up of POROUS TITANIUM PLATE 11, porous carbon fiber paper or carbon cloth successively, cathod catalyst 13, gel flow mutually 14,16 compound compositions of anode catalyst 15, POROUS TITANIUM PLATE.Gel in interior electrode, the external electrode flows phase composition and preparation method with the gel gel of chamber 18 phase that flows that flows mutually.
Embodiment 2:
The weight proportion of each raw material was during gel flowed and prepares mutually:
CH 3OH 40％
H 2SO 4 20％
H 2O 20％
Heteroacid 5%
Conducting polymer 3%
Metallo-organic compound or slaine 12%.Conducting polymer is polyaniline (or polypyrrole).
All the other are with embodiment 1.
Embodiment 3:
The weight proportion of each raw material was during gel flowed and prepares mutually:
CH 3OH 50％
H 2SO 4 10％
H 2O 10％
Heteroacid 10%
Conducting polymer 5%
Metallo-organic compound or slaine 15%.
All the other are with embodiment 2.
Embodiment 4:
The weight proportion of each raw material was during gel flowed and prepares mutually:
CH 3OH 50％
H 2SO 4 10％
H 2O 10％
Heteroacid 10%
Conducting polymer 2%
Metal dust 3%
Metallo-organic compound or slaine 15%.
All the other are with embodiment 2.

Claims (3)

1, a kind of direct methanol fuel cell, it is characterized in that: comprise battery case, external electrode is set in the battery case, external electrode is connected by pad with battery case, and between external electrode and the battery case air chamber is set, interior electrode is set, the gel chamber mutually of flowing is set between interior electrode and the external electrode in the external electrode inboard, in interior electrode inboard air chamber is set, wherein gel flows and is made by following raw materials by weight percent:
CH 3OH 5～60％
H 2SO 4 10～30％
H 2O 20～60％
Heteroacid 3～10%
Conducting polymer and/or metal dust 2～6%
Metallo-organic compound or slaine 5～30%; It is to make by following method mutually that described gel flows: with metallo-organic compound or slaine is presoma, methyl alcohol in flowing mutually is decentralized medium, add sulfuric acid, water, form colloidal sol through hydrolysis, polycondensation reaction, and further mix heteroacid, polymer and/or metal dust are made the mobile phase of gel;
Described metallo-organic compound is titanate ester or silicate class, and slaine is a sodium metasilicate; Described heteroacid is perfluorinated sulfonic acid, phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid or phosphor tin acid.
2, direct methanol fuel cell according to claim 1 is characterized in that: interior electrode successively by POROUS TITANIUM PLATE, anode catalyst, gel flow phase, cathod catalyst, diffusion layer, POROUS TITANIUM PLATE is compound forms; External electrode successively by POROUS TITANIUM PLATE, diffusion layer, cathod catalyst, gel flow phase, anode catalyst, POROUS TITANIUM PLATE is compound forms; The mobile phase composition of gel in external electrode, the interior electrode is flowed mutually identical with the preparation method with the gel of the mobile phase chamber of gel.
3, direct methanol fuel cell according to claim 1 and 2 is characterized in that: conducting polymer is polyaniline or polypyrrole, and metal dust is Cu, Ag or Au powder.
CNB2007100237888A 2007-07-11 2007-07-11 New type direct methanol fuel cell Expired - Fee Related CN100536211C (en)

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CN100536211C true CN100536211C (en) 2009-09-02

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2586091A1 (en) * 2010-06-22 2013-05-01 Basf Se Electrodes and production and use thereof
CN109921077A (en) * 2017-12-12 2019-06-21 中国科学院大连化学物理研究所 A kind of organic/inorganic composite film and preparation and application
CN108923054B (en) * 2018-06-05 2021-08-03 上海交通大学 Membrane-free oxygen-free direct methanol fuel cell
CN111323467B (en) * 2018-12-13 2021-07-20 中国科学院大连化学物理研究所 Elimination of SO in methanol crossover pair DMFC cathode2Method for detecting poisoning behaviors

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