CN1450677A - Air electrode - Google Patents

Air electrode Download PDF

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Publication number
CN1450677A
CN1450677A CN02132701A CN02132701A CN1450677A CN 1450677 A CN1450677 A CN 1450677A CN 02132701 A CN02132701 A CN 02132701A CN 02132701 A CN02132701 A CN 02132701A CN 1450677 A CN1450677 A CN 1450677A
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cobalt
hydroxide
air
layer
polytetrafluoroethylene
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CN1303708C (en
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刘杰
高成和
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Huacheng New Energy Electric Control Co ltd Jilin Prov
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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Abstract

The invention relates to an air electrode, which consists of a catalytic active layer, a current collector, a hydrophobic breathable layer with a stretching direction and a leak-proof sealing layer with the stretching direction vertical to the stretching direction of the hydrophobic breathable layer in sequence, and is manufactured by adopting a rolling type.

Description

A kind of air electrode
Technical field:
The invention belongs to technical field of electrochemistry, in particular a kind of air electrode that is applied in metal-air cell.
Background technology:
Metal-air cell is to make negative pole with the negative metal of electrode potential such as magnesium, aluminium, zinc, cadmium, iron etc., makes anodal active material with airborne oxygen or pure oxygen, and electrolyte generally adopts alkalescence or neutral electrolyte aqueous solution.If when adopting the more negative lithium of electrode potential, sodium, calcium etc. to make negative pole, can only adopt the organic bath or the inorganic electrolyte solution of non-water.
The main feature of metal-air cell is: first, because the used active material of air electrode is an inexhaustible oxygen in the air, so the specific energy height, its theoretical specific energy is generally all more than 1000wh/kg, the actual specific energy belongs to the high-energy chemistry power supply more than 100wh/kg; The second, stable performance, particularly zinc-air cell can be worked under very high current density after adopting powdery porous zinc electrodes and alkaline electrolyte, if adopt pure oxygen to replace air, discharge performance can also increase substantially; The 3rd, low price.
According to the difference of discharge rate, zinc-air cell can be applied to different occasions.It can be used for national defence by the very high zinc-silver battery of displacement cost, as torpedo, guided missile etc.Button zinc-air cell for the work of little electric current long-life can be used for occasions such as wrist-watch, hearing aids and calculator.In, low current density down work can be used for railway signal, radio communication, navigation light, agricultural black light lamp etc. and make power supply.High current density work can be used for vehicle power source, has advantages such as noiseless, non-exhaust emission, is one of first-selected power supply of a kind of up-and-coming green electric motor car.
The conventional air electrode is composited by catalytic active layer, collector conductive mesh, hydrophobic air-permeable layer, collector conductive layer multiple pressure is on the catalytic active layer or be pressed between hydrophobic air-permeable layer and the catalytic active layer, and the hydrophobic air-permeable layer is divided into two kinds of polytetrafluoroethylene type and polyethylene.The air electrode of this structure exists the problems such as carbonating of bad mechanical strength, electrolyte omission or volatilization and electrolyte, has influenced the performance of battery and has limited its application.
Summary of the invention:
Technical problem to be solved by this invention provide a kind of simple in structure, mechanical strength good, the stream of air is controlled, can reduce the become estranged air electrode of carbon dioxide influence of electrolyte stream, to improve the useful life and the storage life of metal-air cell.
Technical scheme of the present invention is: it is successively by forming with the lower part:
By one or more catalytic active layers that constitute in the granular materials such as activated carbon, carbon fibre, graphite, molecular sieve or zeolite of catalyst, polytetrafluoroethylene and high surface; By corrosion resistant metals such as stainless steel, nickel plating mild steel, gold, silver, nickel, tungsten or copper with collector netted or that the cellular form constitutes; The leakproof seal layer that is made of polymer that hydrophobic air-permeable layer with draw direction that is made of the pure film of polytetrafluoroethylene or polytetrafluoroethylene and carbon black and draw direction and hydrophobic air-permeable layer are perpendicular, catalytic active layer, collector, hydrophobic air-permeable layer and leakproof seal layer adopt roll extrusion to form.
Catalyst can be noble metals such as silver, platinum; Can be metal oxides such as manganese dioxide, silver oxide or cobalt oxide; Can be metal hydroxidess such as nickel hydroxide, cobalt hydroxide, iron hydroxide, NaOH, manganous hydroxide, silver hydroxide or chromium hydroxide; Also can be that central metal atom is cobalt, iron, nickel and manganese, ligand be the metallo-chelates such as phthalocyanine cobalt, tetraphenylporphyrin cobalt or tetramethoxy phenyl Cobalt Porphyrin of phthalocyanine, porphyrin; It can also be calcium titanium stone type composite oxide.
The leakproof seal layer is one or more the mixture in polytetrafluoroethylene, polypropylene, polyethylene, polyvinyl chloride, nylon or the Teflon film.
Good effect of the present invention is as follows:
1. as the control mode of a kind of air (oxygen), can avoid the omission or the evaporation of electrolyte, therefore storage life and the aerial exposure lifetimes that has prolonged metal-air cell.
2. improve the mechanical strength of air electrode, helped the machining of metal-air cell.
3. stop and reduced entering of Carbon Dioxide in Air, slowed down the carbonating of alkaline electrolyte, the raising of the internal resistance of cell and the generation of negative pole self discharge have been avoided, the capacity and the life-span that have kept battery, can under high relatively temperature and humidity condition, present good discharge performance, metal-air cell technical application be changed into be possible.
Description of drawings:
Fig. 1 is a section of structure of the present invention.
Embodiment:
With reference to Fig. 1, the present invention is made up of the perpendicular leakproof seal layer 4 of catalytic active layer 1, collector 2, the hydrophobic air-permeable layer 3 with draw direction and draw direction and hydrophobic air-permeable layer 3 draw directions successively, the employing rolling-type is made, earlier make catalytic active layer 1, collector 2, hydrophobic air-permeable layer 3 and leakproof seal layer 4 respectively, pressing forms again.Catalytic active layer 1 is made of in the granular materials such as activated carbon, carbon fibre, graphite, molecular sieve or zeolite of catalyst, polytetrafluoroethylene and high surface one or more, and catalyst can be noble metals such as silver, platinum; Can be metal oxides such as manganese dioxide, silver oxide or cobalt oxide; Can be metal hydroxidess such as nickel hydroxide, cobalt hydroxide, iron hydroxide, NaOH, manganous hydroxide, silver hydroxide or chromium hydroxide; Also can be that central metal atom is cobalt, iron, nickel and manganese, ligand be the metallo-chelates such as phthalocyanine cobalt, tetraphenylporphyrin cobalt or tetramethoxy phenyl Cobalt Porphyrin of phthalocyanine, porphyrin; It can also be calcium titanium stone type composite oxide.Collector 2 generally is to be made of with mesh grid, stretching nets or punching form such as draw in the net corrosion resistant metals such as stainless steel, nickel plating mild steel, gold, silver, nickel, tungsten or copper.Hydrophobic air-permeable layer 3 is made of the pure film of polytetrafluoroethylene or polytetrafluoroethylene and carbon black.Leakproof seal layer 4 is one or more the mixtures in polytetrafluoroethylene, polypropylene, polyethylene, polyvinyl chloride, nylon or the Teflon film.Hydrophobic air-permeable layer 3 and leakproof seal layer 4 can extend on a certain direction and be orientated under certain force-extension, will produce different aperture on level and the vertical direction.Therefore, vertical each other hydrophobic air-permeable layer 3 of the direction of orientation that is drawn into through different directions and leakproof seal layer 4 omission or the volatilization that can prevent electrolyte effectively.Can select the size and the shape in aperture by the control hot strength,, stop the influence of moisture and carbon dioxide, guarantee the capacity and the performance of metal-air cell, improve its storage life and useful life so that regulate and control the path of air effectively.
Embodiment 1
200 gram tetraphenylporphyrin cobalts with after 1000 gram activated carbon mix, were heated 5 hours under 700 ℃ of inert nitrogen protections, add 20% polytetrafluoroethylene binding agent and the stirring of 10 kg of water 3 hours again, be rolled into the catalytic membrane that thickness is about 0.1mm at 10Mpa.Collector uses the conduction nickel screen.The hydrophobic air-permeable layer is that the mixed liquor with carbon black and 20% polytetrafluoroethylene spreads upon on the nylon membrane of simple tension drying.The leakproof seal layer uses the Teflon film vertical with hydrophobic air-permeable layer draw direction.In the compressing tablet film, put into no glycerine glassine paper, put into leakproof seal layer, hydrophobic air-permeable layer, conducting matrix grain and catalytic membrane successively, then glassine paper is covered on the catalytic membrane, extrusion forming under heating, 10Mpa under 260 ℃, being cut into area is 100cm 2Air electrode.With the test that polarizes of stable state constant current, current density is about 100mA/cm under the polarization potential of 1.0V 2, 5 times of the storage lives of prolongation battery.
Embodiment 2
After 300 gram manganese nitrates and 200 are restrained activated carbon and mix; heating is 8 hours under 900 ℃ of inert nitrogen protections; obtain the carbon dust of 280 gram manganese oxides, add 250 gram TritonX-100 binding agents and 5 kg of water again and stirred 3 hours, be rolled into the catalytic membrane that thickness is about 0.15mm at 8Mpa.Collector uses the conduction nickel screen.The hydrophobic air-permeable layer is the Teflon film of simple tension, and the leakproof seal layer uses the Teflon film vertical with hydrophobic air-permeable layer draw direction.In the compressing tablet film, put into no glycerine glassine paper, put into leakproof seal layer, hydrophobic air-permeable layer, conducting matrix grain and catalytic membrane successively, then glassine paper is covered on the catalytic membrane, extrusion forming under heating, 8Mpa under 260 ℃, being cut into area is 100cm 2Air electrode.With the test that polarizes of stable state constant current, current density is about 120mA/cm under the polarization potential of 1.0V 2, 5 times of the storage lives of prolongation battery.

Claims (4)

1, a kind of air electrode is characterized in that: it is successively by forming with the lower part:
By one or more catalytic active layers that constitute (1) in the granular materials such as activated carbon, carbon fibre, graphite, molecular sieve or zeolite of catalyst, polytetrafluoroethylene and high surface; By corrosion resistant metals such as stainless steel, nickel plating mild steel, gold, silver, nickel, tungsten or copper with collector (2) netted or that the cellular form constitutes; The leakproof seal layer (4) that is made of polymer that hydrophobic air-permeable layer (3) with draw direction that is made of the pure film of polytetrafluoroethylene or polytetrafluoroethylene and carbon black and draw direction and hydrophobic air-permeable layer are perpendicular, catalytic active layer (1), collector (2), hydrophobic air-permeable layer (3) and leakproof seal layer (4) adopt roll extrusion to form.
2, a kind of air electrode according to claim 1 is characterized in that: the catalyst in the catalytic active layer (1) can be noble metals such as silver, platinum; Can be metal oxides such as manganese dioxide, silver oxide or cobalt oxide; Can be metal hydroxidess such as nickel hydroxide, cobalt hydroxide, iron hydroxide, NaOH, manganous hydroxide, silver hydroxide or chromium hydroxide; Also can be that central metal atom is cobalt, iron, nickel and manganese, ligand be the metallo-chelates such as phthalocyanine cobalt, tetraphenylporphyrin cobalt or tetramethoxy phenyl Cobalt Porphyrin of phthalocyanine, porphyrin; It can also be calcium titanium stone type composite oxide.
3, a kind of air electrode according to claim 1 is characterized in that: collector (2) constitutes with mesh grid, stretching nets or punching form such as draw in the net,
4, a kind of air electrode according to claim 1 is characterized in that: leakproof seal layer (4) is one or more the mixture in polytetrafluoroethylene, polypropylene, polyethylene, polyvinyl chloride, nylon or the Teflon film.
CNB021327017A 2002-07-31 2002-07-31 Air electride Expired - Fee Related CN1303708C (en)

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1306637C (en) * 2004-11-11 2007-03-21 南亚塑胶工业股份有限公司 Air electrode of multi-layer sintering structure and its manufacturing method
CN100562353C (en) * 2004-10-21 2009-11-25 松下电器产业株式会社 Oxygen-permeable film, oxygen see through sheet and comprise their battery
CN101197444B (en) * 2006-12-08 2010-06-16 比亚迪股份有限公司 Air electrode, and method and device for producing the same
CN101388446B (en) * 2007-09-11 2010-10-27 戴志强 Three-dimensional electrode for accummulater and preparing mehtod
CN101882682A (en) * 2009-05-04 2010-11-10 协盈电子工业股份有限公司 Method for manufacturing flexible cathode electrode sheet
CN101971411A (en) * 2009-05-19 2011-02-09 丰田自动车株式会社 Air cell
CN102283644A (en) * 2011-05-31 2011-12-21 青岛光电医疗科技有限公司 Disposable hidden line integrated electrode and connector
CN102447115A (en) * 2010-12-31 2012-05-09 山东理工大学 Novel magnesium air battery cathode
CN103199272A (en) * 2013-04-16 2013-07-10 南京大学 Simple preparation method of integrated metal-air cathode for metal-air battery
US9184449B2 (en) 2004-10-21 2015-11-10 Panasonic Intellectual Property Management Co., Ltd. Oxygen permeable film, oxygen permeable sheet, and cell including these
CN105696018A (en) * 2016-01-18 2016-06-22 天津大学 Preparation and application of graphite-carbon black mixed air diffusion cathode
CN105810954A (en) * 2016-04-05 2016-07-27 扬州大学 Active carbon air negative electrode and preparation method thereof
CN104538706B (en) * 2014-12-06 2016-09-14 云南冶金集团创能铝空气电池股份有限公司 Aluminum-air battery air electrode that a kind of manganese dioxide carbon back is silver-plated and preparation method thereof
CN106207192A (en) * 2015-12-02 2016-12-07 昆明理工大学科技园有限公司 There is carbon dioxide filter and inhale the metal-air battery electrode of layer
CN106684392A (en) * 2016-11-21 2017-05-17 深圳海能动力控股有限公司 Cathode-air electrode, hydroelectric generation metal-air battery and preparation method
CN108701885A (en) * 2016-03-17 2018-10-23 株式会社电装 Lithium-air battery system
CN110085874A (en) * 2012-10-09 2019-08-02 氧动能有限责任公司 Electrode assembly and preparation method thereof
CN111326746A (en) * 2020-03-03 2020-06-23 武汉睿亿新能源科技有限责任公司 Preparation method of air electrode
CN111446454A (en) * 2020-04-20 2020-07-24 上海交通大学 Application of electronic compound as lithium-air battery anode catalyst material

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* Cited by examiner, † Cited by third party
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CN109755503B (en) * 2018-12-13 2021-09-07 温州大学 Preparation method of manganese compound/carbon tube sulfur-carrying composite material and application of manganese compound/carbon tube sulfur-carrying composite material in lithium-sulfur battery

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US5418080A (en) * 1994-07-01 1995-05-23 Electric Fuel (E.F.L.) Ltd. Mechanically rechargeable, electrochemical metal-air battery
US5506067A (en) * 1995-04-04 1996-04-09 Aer Energy Resources, Inc. Rechargeable electrochemical cell and cell case therefor with vent for use in internal recombination of hydrogen and oxygen
CN1253385A (en) * 1998-11-07 2000-05-17 孙法炯 Air electrode and metal-air battery made of same
CN1150651C (en) * 1998-11-15 2004-05-19 孙法炯 Cylindrical metal-air battery

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100562353C (en) * 2004-10-21 2009-11-25 松下电器产业株式会社 Oxygen-permeable film, oxygen see through sheet and comprise their battery
US9184449B2 (en) 2004-10-21 2015-11-10 Panasonic Intellectual Property Management Co., Ltd. Oxygen permeable film, oxygen permeable sheet, and cell including these
CN1306637C (en) * 2004-11-11 2007-03-21 南亚塑胶工业股份有限公司 Air electrode of multi-layer sintering structure and its manufacturing method
CN101197444B (en) * 2006-12-08 2010-06-16 比亚迪股份有限公司 Air electrode, and method and device for producing the same
CN101388446B (en) * 2007-09-11 2010-10-27 戴志强 Three-dimensional electrode for accummulater and preparing mehtod
CN101882682A (en) * 2009-05-04 2010-11-10 协盈电子工业股份有限公司 Method for manufacturing flexible cathode electrode sheet
US8802302B2 (en) 2009-05-19 2014-08-12 Toyota Jidosha Kabushiki Kaisha Air battery including oxygen-containing solvent
CN101971411A (en) * 2009-05-19 2011-02-09 丰田自动车株式会社 Air cell
CN101971411B (en) * 2009-05-19 2013-03-13 丰田自动车株式会社 Air cell
CN102447115A (en) * 2010-12-31 2012-05-09 山东理工大学 Novel magnesium air battery cathode
CN102447115B (en) * 2010-12-31 2013-08-14 山东理工大学 Magnesium air battery cathode
CN102283644A (en) * 2011-05-31 2011-12-21 青岛光电医疗科技有限公司 Disposable hidden line integrated electrode and connector
CN110085874A (en) * 2012-10-09 2019-08-02 氧动能有限责任公司 Electrode assembly and preparation method thereof
CN103199272A (en) * 2013-04-16 2013-07-10 南京大学 Simple preparation method of integrated metal-air cathode for metal-air battery
CN104538706B (en) * 2014-12-06 2016-09-14 云南冶金集团创能铝空气电池股份有限公司 Aluminum-air battery air electrode that a kind of manganese dioxide carbon back is silver-plated and preparation method thereof
CN106207192A (en) * 2015-12-02 2016-12-07 昆明理工大学科技园有限公司 There is carbon dioxide filter and inhale the metal-air battery electrode of layer
CN105696018A (en) * 2016-01-18 2016-06-22 天津大学 Preparation and application of graphite-carbon black mixed air diffusion cathode
CN105696018B (en) * 2016-01-18 2018-09-04 天津大学 A kind of preparation and application of graphite-carbon black mixing air dispenser cathode piece
CN108701885A (en) * 2016-03-17 2018-10-23 株式会社电装 Lithium-air battery system
CN108701885B (en) * 2016-03-17 2021-04-30 株式会社电装 Lithium air battery system
CN105810954A (en) * 2016-04-05 2016-07-27 扬州大学 Active carbon air negative electrode and preparation method thereof
CN106684392A (en) * 2016-11-21 2017-05-17 深圳海能动力控股有限公司 Cathode-air electrode, hydroelectric generation metal-air battery and preparation method
CN111326746A (en) * 2020-03-03 2020-06-23 武汉睿亿新能源科技有限责任公司 Preparation method of air electrode
CN111446454A (en) * 2020-04-20 2020-07-24 上海交通大学 Application of electronic compound as lithium-air battery anode catalyst material

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