CN103825031A - Self-breathing type negative structure of alcohol fuel battery - Google Patents

Self-breathing type negative structure of alcohol fuel battery Download PDF

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Publication number
CN103825031A
CN103825031A CN201410098387.9A CN201410098387A CN103825031A CN 103825031 A CN103825031 A CN 103825031A CN 201410098387 A CN201410098387 A CN 201410098387A CN 103825031 A CN103825031 A CN 103825031A
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China
Prior art keywords
self
fuel battery
alcohol fuel
battery according
breathing
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CN201410098387.9A
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Chinese (zh)
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CN103825031B (en
Inventor
刘晓为
袁玮健
张雪林
张宇峰
王志刚
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CETC Information Science Research Institute
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Harbin Institute of Technology
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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
    • H01M4/8621—Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0232—Metals or alloys
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Ceramic Engineering (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

The invention provides a self-breathing type negative structure of an alcohol fuel battery for solving the problem that a self-breathing channel of a negative plate is blocked due to flooding. The negative plate of the alcohol fuel battery is made of an aluminum alloy material, a self-breathing through hole is formed in the negative plate, a thin gold layer covers a contact part between the surface of the negative plate and a membrane electrode, and an oxide ceramic membrane with super-hydrophilicity is prepared at a part in contact with air by the micro-arc oxidation technology. The self-breathing type negative structure of the alcohol fuel battery solves the problem that the self-breathing channel is blocked due to blooding of the negative, can improve the oxygen gas transferring effect, and further improve the output performance of the alcohol fuel battery.

Description

A kind of self-respiration type cathode construction of alcohol fuel battery
Technical field
The invention belongs to Proton Exchange Membrane Fuel Cells field, be specifically related to a kind of design of self-respiration type cathode construction of alcohol fuel battery.
Background technology
Direct alcohol fuel cell (Direct Methanol Fuel Cell ﹣ DMFC) is using methyl alcohol, ethanol, dimethyl ether etc. as fuel, have simple in structure, conversion efficiency is high, can cold-starting etc. advantage, have good application prospect in microminiature portable product field.Particularly self-respiration type alcohol fuel battery, due to the cancellation of active additional device, its compact conformation, is therefore applicable to the portable and microminiature equipment application of low power requirements (<10W) more.In actual applications, the minus plate of self-breathing type direct alcohol fuel cell not only plays a part to collect cathode current, and is the transmission channel of negative electrode oxygen and water.Airborne oxygen participates in reaction from respiration channel through diffusing into inside battery by minus plate; The water that cathode reaction produces and the water that is penetrated into negative electrode from anode can be transferred to certainly exhaling perhaps in passage of negative electrode by cathode catalysis layer under capillarity, then rely on natural evaporation and gravity to discharge.In this course, be easy to occur liquid water in the accumulation in respiration channel, thereby hinder reaching of oxygen, particularly, in the time of heavy-current discharge, negative electrode likely stops up completely from respiration channel, thereby has seriously reduced performance and the stability of battery.
Summary of the invention
The object of this invention is to provide a kind of self-respiration type cathode construction of alcohol fuel battery, it has strengthened the drainability of minus plate, has solved because liquid water blocks the problem of minus plate from respiration channel.
Described object is achieved by the following scheme:
A self-respiration type cathode construction for alcohol fuel battery, comprises the cathode plate that aluminum alloy materials is made, and is provided with the through hole for " certainly breathing " above cathode plate; The part directly contacting with membrane electrode on cathode plate surface adopts the method for plating or magnetron sputtering to cover layer of gold layer, prevents from corroding and reducing contact resistance; On cathode plate surface, directly the part of ingress of air adopts differential arc oxidization technique making one deck to have the membrane of oxide ceramics of Superhydrophilic.Because this ceramic membrane has super hydrophilic characteristic, the water that negative electrode is produced can diffuse into rapidly on the surface of ceramic membrane a plane, prevents that it from forming liquid water droplets, thus effectively avoid cathode plate water logging.
The present invention has the following advantages:
(1) the cathode plate percent opening of the percent opening of cathode plate and conventional batteries remains unchanged, but due to the existence of super hydrophilic thin layer, makes the water of negative electrode in respiration channel cannot form water droplet, thereby avoided the blockage problem from spiracle;
(2) utilize differential arc oxidization technique, can guarantee prepared super hydrophilic membrane part complete, that covered cathode plate surface contacts with air uniformly, and there is good adhesion between this super hydrophilic membrane and substrate, also can significantly improve the corrosion resistance of pole plate simultaneously.
accompanying drawing explanation:
Fig. 1 is the STRUCTURE DECOMPOSITION schematic diagram of passive direct methanol fuel cell in the present invention;
Fig. 2 is the cathode plate back side (contacting a side with membrane electrode) gold layer schematic diagram;
Fig. 3 is cathode plate front (contacting a side with air) membrane of oxide ceramics schematic diagram;
Fig. 4 has the direct methanol fuel cell of cathode construction of the present invention and conventional cathode structure at 100mA/cm 2current density under Discharge test;
Fig. 5 is at 100mA/cm 2current density under through the photo from respiration channel of the conventional cathode structure after long-time electric discharge;
Fig. 6 is at 100mA/cm 2current density under through the photo from respiration channel of the cathode construction in the present invention after long-time electric discharge.
In Fig. 1-Fig. 3: 1-fuel cavity; 2-plate; 3-insulation cushion; 4-membrane electrode; 5-cathode plate; 6-through hole; 7-gold layer; 8-has the membrane of oxide ceramics of super water-wet behavior.
embodiment:
Embodiment one: present embodiment adopts aluminium alloy to carry out the making of cathode plate as shown in Figures 2 and 3, after employing alcohol or acetone carry out oil removal treatment, put it in the working solution that contains sodium metasilicate (5-15g/mL) and inferior sodium phosphate (0.5-2g/mL), and using it as positive pole, using work nest as negative pole, controlling working solution temperature below 50 degree, is that 400-600V, negative-going pulse voltage are to process 10-120 minute under 0-300V, the pulse frequency condition that is 10-5000Hz at bidirectional pulse power supply, direct impulse voltage; The cathode plate that differential arc oxidation was processed is rinsed well with running water, and the ceramic coating formed by micro-arc oxidation of the part then its surface being contacted with membrane electrode polishes off, and adopts the mode of magnetron sputtering or plating at this part surface deposition layer of gold layer.
Utilize fixture to be fixed on a place according to the order shown in Fig. 1 the cathode plate of processing and plate, membrane electrode, insulation cushion and liquid storage cylinder, can be used as a complete monocell.Under room temperature, adopt the methyl alcohol of 2M at 100mA/cm 2current density under carry out discharge test, the results are shown in Figure 4.As shown in Figure 5, traditional cathode construction there is soon water logging from respiration channel, and there is not the water logging phenomenon from respiration channel in cathode construction of the present invention in whole discharge process, as shown in Figure 6.Therefore, in Fig. 4, the battery discharge voltage of conventional cathode structure is decayed fast, and it is very steady to have the battery discharge voltage of cathode construction of the present invention.
Embodiment two: the difference of present embodiment and embodiment one is, sodium aluminate and 0.5-2g/mL inferior sodium phosphate that the electrolyte that cathode plate differential arc oxidation adopts while processing is 5-15g/mL.
Embodiment three: the difference of present embodiment and embodiment one is, the power supply that cathode plate differential arc oxidation adopts while processing is DC power supply, processing voltage is 300-600V.
The present invention has been to improve the structure of cell cathode pole plate with respect to the innovative point of prior art., as fuel, oxygen is directly supplied with by atmosphere to adopt the fuel cell of this kind of cathode plate structure still to use rich hydrogen material (hydrogen, methyl alcohol, ethanol etc.).The improvements of target pole plate are, utilize magnetron sputtering or electroplating technology to form the thin layer of layer of gold at the back side of cathode plate (contact membranes electrode one side), in minus plate front, (part of ingress of air) carried out super hydrophilic treated, water is entered in the time of respiration channel can spread rapidly, does not form drop.When battery operated, air enters via the through hole of cathode plate, and negative electrode oxygen and electronics, proton reaction generate water, flow out pole plate by negative electrode duct.Compared with traditional structure, the percent opening of cathode plate of the present invention remains unchanged, but increase the contact area of negative electrode water and air, super hydrophilic treated has been carried out in front at cathode plate, the water that negative electrode is produced can promptly spread, be difficult for forming water droplet, thereby make water evaporate more fully rapidly and to discharge.
The just exemplary illustration to this patent and do not limit its protection range of present embodiment; those skilled in the art can also carry out part to it and change; as long as no the Spirit Essence that exceeds this patent, be all considered as the replacement that is equal to this patent, all within the protection range of this patent.

Claims (6)

1. the self-respiration type cathode construction of an alcohol fuel battery, comprise cathode plate, above cathode plate, be provided with the through hole for " certainly breathing ", it is characterized in that the part that described cathode plate surface contacts with membrane electrode is coated with layer of gold layer, the part contacting with air is coated with one deck and has the membrane of oxide ceramics of super water-wet behavior.
2. the self-respiration type cathode construction of alcohol fuel battery according to claim 1, is characterized in that described gold layer is to adopt the mode of magnetron sputtering or plating to be prepared.
3. the self-respiration type cathode construction of alcohol fuel battery according to claim 1, the membrane of oxide ceramics described in it is characterized in that with super water-wet behavior adopts differential arc oxidization technique to prepare.
4. the self-respiration type cathode construction of alcohol fuel battery according to claim 3, is characterized in that the power supply that described differential arc oxidation adopts while processing is DC power supply or AC power.
5. the self-respiration type cathode construction of alcohol fuel battery according to claim 3, contains SiO in the electrolyte adopting while it is characterized in that described differential arc oxidation processing 3 2-or AlO 2 -.
6. the self-respiration type cathode construction of alcohol fuel battery according to claim 1, is characterized in that described cathode plate adopts aluminum alloy materials to be made.
CN201410098387.9A 2014-03-18 2014-03-18 A kind of self-respiration type cathode construction of alcohol fuel battery Active CN103825031B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104087996A (en) * 2014-07-28 2014-10-08 吕鹏翔 Aluminum alloy surface easy-cleaning micro-arc oxidation ceramic membrane layer and preparation method thereof
CN110797560A (en) * 2019-11-08 2020-02-14 重庆大学 Miniature membraneless liquid fuel cell with hydrogel solid electrolyte
CN110808393A (en) * 2019-11-08 2020-02-18 重庆大学 Detachable and packaging pressure-adjustable hydrogel liquid storage and supply type membrane-free fuel cell

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19625617A1 (en) * 1996-06-26 1998-01-08 Siemens Ag High temp. fuel-cell electrodes system
WO2003069712A2 (en) * 2002-02-13 2003-08-21 Creavis Gesellschaft Für Technologie Und Innovation Mbh Proton-conducting ceramic membranes on the basis of zirconium phosphates, method for the production thereof, and use thereof in meas and fuel cells
CN101071880A (en) * 2007-05-21 2007-11-14 哈尔滨工业大学 Serial battery for passive self-breathing direct methanol fuel cell
CN101159333A (en) * 2007-09-28 2008-04-09 哈尔滨工业大学 Self-respiration type fuel battery membrane electrode and method for producing the same
CN101179134A (en) * 2007-11-30 2008-05-14 哈尔滨工业大学 Method of producing thin hydrophile type direct methanol fuel cell membrane electrode
US20080280190A1 (en) * 2005-10-20 2008-11-13 Robert Brian Dopp Electrochemical catalysts
CN102299359A (en) * 2011-08-03 2011-12-28 哈尔滨工业大学 Self-breathing alcohol fuel cell

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19625617A1 (en) * 1996-06-26 1998-01-08 Siemens Ag High temp. fuel-cell electrodes system
WO2003069712A2 (en) * 2002-02-13 2003-08-21 Creavis Gesellschaft Für Technologie Und Innovation Mbh Proton-conducting ceramic membranes on the basis of zirconium phosphates, method for the production thereof, and use thereof in meas and fuel cells
US20080280190A1 (en) * 2005-10-20 2008-11-13 Robert Brian Dopp Electrochemical catalysts
CN101071880A (en) * 2007-05-21 2007-11-14 哈尔滨工业大学 Serial battery for passive self-breathing direct methanol fuel cell
CN101159333A (en) * 2007-09-28 2008-04-09 哈尔滨工业大学 Self-respiration type fuel battery membrane electrode and method for producing the same
CN101179134A (en) * 2007-11-30 2008-05-14 哈尔滨工业大学 Method of producing thin hydrophile type direct methanol fuel cell membrane electrode
CN102299359A (en) * 2011-08-03 2011-12-28 哈尔滨工业大学 Self-breathing alcohol fuel cell

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104087996A (en) * 2014-07-28 2014-10-08 吕鹏翔 Aluminum alloy surface easy-cleaning micro-arc oxidation ceramic membrane layer and preparation method thereof
CN104087996B (en) * 2014-07-28 2016-06-01 大连大学 The preparation method of aluminum alloy surface easy clean property Micro-Arc Oxidized Ceramic Coating
CN110797560A (en) * 2019-11-08 2020-02-14 重庆大学 Miniature membraneless liquid fuel cell with hydrogel solid electrolyte
CN110808393A (en) * 2019-11-08 2020-02-18 重庆大学 Detachable and packaging pressure-adjustable hydrogel liquid storage and supply type membrane-free fuel cell

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Inventor after: Liu Xiaowei

Inventor after: Zhang Xuelin

Inventor after: Yuan Weijian

Inventor after: Zhang Yufeng

Inventor after: Wang Zhigang

Inventor before: Liu Xiaowei

Inventor before: Yuan Weijian

Inventor before: Zhang Xuelin

Inventor before: Zhang Yufeng

Inventor before: Wang Zhigang

COR Change of bibliographic data

Free format text: CORRECT: INVENTOR; FROM: LIU XIAOWEI YUAN WEIJIAN ZHANG XUELIN ZHANG YUFENG WANG ZHIGANG TO: LIU XIAOWEI ZHANG XUELIN YUAN WEIJIAN ZHANG YUFENG WANG ZHIGANG

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Effective date of registration: 20161226

Address after: 100000 Beijing city Haidian District four crossing No. 36 North Building No. 4

Patentee after: INFORMATION SCIENCE RESEARCH INSTITUTE OF CETC

Address before: 150000 Harbin, Nangang, West District, large straight street, No. 92

Patentee before: Harbin Polytechnic Univ.