CN102214827B - Air electrode composite of dual-carrier recombination lithium air battery and preparation method thereof - Google Patents
Air electrode composite of dual-carrier recombination lithium air battery and preparation method thereof Download PDFInfo
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- CN102214827B CN102214827B CN2010102694822A CN201010269482A CN102214827B CN 102214827 B CN102214827 B CN 102214827B CN 2010102694822 A CN2010102694822 A CN 2010102694822A CN 201010269482 A CN201010269482 A CN 201010269482A CN 102214827 B CN102214827 B CN 102214827B
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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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
- H01M4/96—Carbon-based electrodes
Abstract
The invention relates to an air electrode composite of a dual-carrier recombination lithium air battery and a preparation method thereof, and provides the air electrode composite of the dual-carrier recombination lithium air battery. The air electrode composite comprises the following ingredients in parts by total weight: 10-40 parts of first carrier loaded with 5-30 parts of catalysts on the surface, 10-40 parts of second carrier which is subjected to oleophobic property treatment, and 5-20 parts of adhesion agent, wherein the first carrier and the second carrier are the same or different, and are selected from carbon materials, an organic high-molecular polymer, simple substance of metal and the combination of the carbon materials, the organic high-molecular polymer and the simple substance of metal. The invention also provides a preparation method of the air electrode composite of the dual-carrier recombination lithium air battery.
Description
Technical field
The invention belongs to field of chemical power source, relate to air electrode and technology of preparing thereof that a class can be used for the two carrier composite structure of high-performance of lithium air secondary battery positive pole.Specifically, the present invention relates to two compound lithium-air battery air electrode composition and method of making the sames of carrier.
Background technology
In all electrochemical power sources, lithia pneumoelectric pond has the highest energy density, 13200Wh/kg.Principle is metal Li negative pole and positive active material oxygen reaction, changes chemical energy into electric energy.Oxygen need not to be stored in the battery, and is provided by the air in the environment, thereby is also referred to as lithium-air battery.
But the actual capacity of lithium-air battery is restricted by the micro-structural of air electrode.General air electrode mainly is made up of catalyst, catalyst carrier and binding agent three parts.In when discharge, the lithium ion of coming from the negative pole migration in the electrolyte is under the catalytic action that is carried on supported catalyst, and the oxygen that sees through and be adsorbed in catalyst surface active point with side of the positive electrode carries out gas-solid liquid phase reaction.But, because the solubility of product (lithia or lithium peroxide) in solution that obtains is very low, be deposited in the hole of air electrode (mainly being carrier material), the product of deposition stops up air electrode gradually, final isolated electrolyte contacts with oxygen, guiding discharge stops, and influences the actual capacity of lithium-air battery.Therefore, development of new air electrode micro-structural is significant to the development of lithium-air battery.
Based on this, at present the research of lithium-air battery is mainly concentrated on the design of novel air electrode, be intended to alleviate to a certain extent in the air electrode since the obstruction of discharging product to the adverse effect of discharge process.For example, the inhomogeneous deposition of product can form the fine and close product film of one deck on the air electrode surface under high current density, thereby guiding discharge stops, and the result reduces the air electrode utilance.Can improve the specific capacity of lithium-air battery as carrier by the material with carbon element of preparation high porosity, Xia Yongyao etc. (J Solid State Electrochem14 (2010) 109-114) propose " super P carbon black " (Super P carbon black (CB)) of bigger serface as catalyst carrier, under lower discharge rate, obtained result preferably, but when higher current density, the discharging product deposition is inhomogeneous, form the product film of one deck densification on the air electrode surface, the result has stoped the transmission of oxygen to inside, guiding discharge stops, and the air electrode service efficiency is reduced.Xia Yongyao (Chemistry of Materials 19 (2007) 2095-2101) etc. propose with ordered mesopore carbon CMK-3 as catalyst carrier, and think catalyst-free deposition in the part micropore of CMK-3, can remain unimpeded in the discharge process, formed diffusion electrode preferably, but this design does not have generality, is unfavorable for promoting.Therefore, a kind of air electrode structure that has more practicality of design becomes key and the focus of exploitation high-performance lithium air cell.
Up to now, this area is still untapped to be gone out a kind ofly can effectively to alleviate discharging product to the partial occlusion of air electrode when guaranteeing the air electrode height ratio capacity, improves the lithium-air battery air electrode material of lithium-air battery high rate performance and cyclical stability.
Therefore, this area presses for to develop a kind ofly can effectively alleviate discharging product to the partial occlusion of air electrode when guaranteeing the air electrode height ratio capacity, improve the lithium-air battery air electrode material of lithium-air battery high rate performance and cyclical stability.
Summary of the invention
The invention provides a kind of compound lithium-air battery air electrode composition and method of making the same of two carriers of novelty, thereby solved problems of the prior art.
On the one hand, the invention provides a kind of pair of lithium-air battery air electrode composition that carrier is compound, it comprises, in the total weight of described composition:
First carrier of 10-40 weight portion, its area load has the catalyst of 5-30 weight portion;
Second carrier of 10-40 weight portion, it has carried out the oleophobic property processing; And
The 5-20 parts by weight of adhesive;
Wherein, described first carrier and second carrier are identical or different, are selected from: material with carbon element, organic high molecular polymer, elemental metals and their combination.
One preferred embodiment in, described material with carbon element is selected from: acetylene black, active carbon, foamy carbon, ordered mesopore carbon, carbon nano-tube and carbon nano-fiber; Described organic high molecular polymer is selected from: polyaniline, poly-propylamine, polypyrrole, polythiophene, polyacetylene and their derivative; Described elemental metals is selected from: Ni, Al and Ti.
Another preferred embodiment in, described catalyst is selected from: single metal oxide, composite oxide of metal, the metal simple-substance with electrochemical catalysis hydrogen reduction and oxidation activity and their combination.
Another preferred embodiment in, described single metal oxide is selected from: Co
3O
4, MnO
2, Mn
2O
3, CoO, ZnO, V
2O
5, MoO, Cr
2O
3, Fe
3O
4, Fe
2O
3, FeO, CuO and NiO; Described composite oxide of metal is selected from: spinel-type composite oxide of metal, pyrochlore-type composite oxide of metal and perovskite type metal composite oxides; Described metal simple-substance with electrochemical catalysis hydrogen reduction and oxidation activity is selected from: Pt, Au, Ag, Au, Co, Zn, V, Cr, Pd, Rh, Cd, Nb, Mo, Ir, Os, Ru, Ni, their alloy and their combination.
Another preferred embodiment in, described binding agent is selected from: polytetrafluoroethylene, Kynoar, polyethylene, polyethylene glycol oxide, polyacrylonitrile and their copolymer.
Another preferred embodiment in, described first carrier and second carrier are of a size of 50-1000nm, the aperture size that described first carrier and second carrier form is 5-100nm.
On the other hand, the invention provides a kind of pair of lithium-air battery air electrode preparation of compositions method that carrier is compound, this method comprises, in the total weight of described composition:
Provide first carrier of 10-40 weight portion, at the catalyst of its area load 5-30 weight portion;
Second carrier of 10-40 weight portion is provided, it is carried out oleophobic property handle; And
The first treated carrier and second carrier are evenly mixed with the 5-20 parts by weight of adhesive by 5/1 to 1/10 weight ratio, obtain two compound lithium-air battery air electrode compositions of carrier,
Wherein, described first carrier and second carrier are identical or different, are selected from: material with carbon element, organic high molecular polymer, elemental metals and their combination.
One preferred embodiment in, the mode of loading of described catalyst is selected from: carrier surface in-situ chemical reaction deposition, infusion process, electroplating deposition and physical vapor deposition.
Another preferred embodiment in, described catalyst cupport thickness is 0.5-50nm.
Another preferred embodiment in, described oleophobic property is handled and is selected from: acid treatment, water treatment and polarity are handled.
Again on the one hand, the invention provides a kind of lithium-air battery with anodal, it comprises the above-mentioned pair of lithium-air battery air electrode composition that carrier is compound.
Another aspect the invention provides a kind of lithium-air battery, and it comprises above-mentioned lithium-air battery and uses anodal as air electrode.
Description of drawings
Fig. 1 is TEM (transmission electron microscope) photo of the carrier material CMK-3 that uses among the embodiment 1-2.
Fig. 2 is the first charge-discharge curve of the composite electrode of gained among Comparative Examples 1, embodiment 1 and the embodiment 2, shows the variation relation of specific capacity and voltage.
Embodiment
The present inventor finds after having passed through extensive and deep research, at the local air electrode that stops up of the anodal insoluble product of lithium-air battery in the prior art, reduce the utilance of air electrode hole, thereby cause the loss of capacity, reduce problems such as cycle performance and high rate performance, utilize two compound modes of carrier, with the catalyst uniform load in a part of carrier wherein, and the load of another part carrier catalyst-free, when discharge, no product deposition in the carrier material hole of catalyst-free load, can guarantee all the time that the transmission channel of oxygen is unimpeded, thereby prepare a kind of high efficiency lithium-air battery diffusion electrode that it can be when guaranteeing the air electrode height ratio capacity, effectively alleviate discharging product to the partial occlusion of air electrode, improve lithium-air battery high rate performance and cyclical stability.Based on above-mentioned discovery, the present invention is accomplished.
In a first aspect of the present invention, a kind of pair of lithium-air battery air electrode composition that carrier is compound is provided, it comprises, in the total weight of described composition:
First carrier of 10-40 weight portion, its area load has the catalyst of 5-30 weight portion;
Second carrier of 10-40 weight portion, it has carried out the oleophobic property processing; And 5-20 parts by weight of adhesive.
In the present invention, described first carrier and second carrier can be identical materials, also can be different materials, the perhaps combination of multiple material, be selected from: material with carbon element, for example acetylene black, active carbon, foamy carbon, ordered mesopore carbon, carbon nano-tube, carbon nano-fiber etc.; Other have the organic high molecular polymer of good electron conductivity, for example polyaniline, poly-propylamine, polypyrrole, polythiophene, polyacetylene and their derivative; And elemental metals, for example Ni, Al, Ti etc.In order to obtain chemically stable high-performance composite air electrode, for the selection principle of carrier be: high porosity, high-specific surface area, have preferably compatibility with catalyst and organic electrolyte, chemical property is stable, electron conduction is good.
Preferably, the optimal size of described first carrier and second carrier is 50-1000nm, and the optimal size in the aperture of formation is 5-100nm.
In the present invention, described catalyst can be single metal oxide, as Co
3O
4, MnO
2, Mn
2O
3, CoO, ZnO, V
2O
5, MoO, Cr
2O
3, Fe
3O
4, Fe
2O
3, FeO, CuO, NiO etc.; Composite oxide of metal (spinel-type, pyrochlore-type or Ca-Ti ore type etc.); One class that also can expand to other has the metal simple-substance of electrochemical catalysis hydrogen reduction and oxidation activity (for example, Pt, Au, Ag, Au, Co, Zn, V, Cr, Pd, Rh, Cd, Nb, Mo, Ir, Os, Ru, Ni etc.) and alloy thereof etc.; It also can be the combination of multiple catalyst material.For obtaining two carrier gas electrodes of better performances, for the selection of catalysts principle be: synthesis technique is simple and easy, pattern is controlled, cost is low, oxygen evolution reaction and oxygen reduction reaction are all had catalytic activity preferably.
In the present invention, described binding agent can polytetrafluoroethylene (PTFE), Kynoar (PVDF), polyethylene (PE), polyethylene glycol oxide (PEO), polyacrylonitrile (PAN) etc. and their copolymer.
In a second aspect of the present invention, a kind of pair of lithium-air battery air electrode preparation of compositions method that carrier is compound is provided, this method may further comprise the steps:
(1) provides first carrier, at its catalyst supported on surface;
(2) provide second carrier, it is carried out oleophobic property handle; And
(3) handle second carrier that obtains in first carrier that obtains and the step (2) by the weight ratio (first carrier/second carrier=5/1 is to 1/10) of optimum with handling in the step (1), and the adding binding agent carries out the compound lithium-air battery air electrode composition that obtains.
In the present invention, the mode of loading of described catalyst is carrier surface in-situ chemical reaction deposition, also can adopt methods such as infusion process, electroplating deposition, physical vapor deposition, selection principle for the catalyst cupport mode is: catalyst is uniformly dispersed at carrier surface, thickness is suitable, and the catalyst pattern is controlled.
Preferably, described catalyst is 0.5-50nm in the optimal thickness of carrier surface load.
In the present invention, described oleophobic property processing mode can be acid treatment, water treatment, polarity processing etc.
In a third aspect of the present invention, provide a kind of lithium-air battery of the compound lithium-air battery air electrode composition of the above-mentioned pair of carrier that comprises with anodal.
In a fourth aspect of the present invention, provide a kind of anodal lithium-air battery as air electrode of above-mentioned lithium-air battery that comprises.
The excellent characteristics of the two carrier composite air electrodes for lithium-air battery of the present invention comprises:
(1) catalyst is carried on first carrier surface equably;
(2) size of catalyst and carrier is scattered in the air electrode as active material between nanometer and sub-micron equably;
(3) discharge capacity of air electrode can be regulated by the size that forms hole after the first carrier supported catalyst amount in the air electrode and the load;
(4) electrochemical properties of novel pair of carrier composite structure electrode possesses the chemical property of lithium-air battery, has higher discharge capacity first, has high rate performance and good electrochemistry cyclical stability preferably.
Compare with existing various lithium-air battery air electrode materials and preparation method thereof, major advantage of the present invention is:
(1) first surfaces of carrier materials uniform load the electrochemical redox catalyst of high catalytic activity, and another part second carrier catalyst-free;
(2) catalyst is distributed in the surface of first carrier equably, can improve the service efficiency of catalyst, and can reduce the use amount of inert matter binding agent;
(3) deposition of no anodal product in the duct that forms of second carrier of catalyst-free load remains unimpededly in discharge process, provides required passage for oxygen transmits incessantly;
(4) second carriers have certain oleophobic property, can prevent from being flooded by electrolyte, guarantee to remain in discharge process unimpeded;
(5) first carriers and second carrier are evenly distributed on the whole, and the passage that second carrier is formed can be transported to oxygen each microcosmos area of air electrode, thereby can alleviate the product partial occlusion to the full extent and the capacitance loss that causes;
(6) at 0.1mA/cm
2Discharge rate under, obtained the specific discharge capacity that significantly improves than single carrier electrode, reach 1286mAh/g;
(7) preparation method is simple, and cost is low, is fit to large-scale industrial production;
(8) raw material sources are extensive.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.But, should be understood that these embodiment only are used for explanation the present invention and do not constitute limitation of the scope of the invention.The test method of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Except as otherwise noted, all percentage and umber are by weight.
Comparative Examples 1:
Catalyst manganese dioxide (EMD) and acetylene black and Kynoar (PVDF) are made slurry by 19: 11: 15 weight ratio in N-methyl pyrrolidone (NMP) medium, coat collector Ni on the net and carry out drying, make electrode film thus as positive pole.Be negative pole with the metallic lithium foil, U.S. Celgard company polypropylene screen is barrier film, 1M LiPF
6/ PC is electrolyte, in the voltage range of 2-4.5V, and 0.1mA/cm
2Current density under discharge and recharge test, active material is the quality of material with carbon element in the air electrode.The gained result of the test is as shown in table 1 below.
Embodiment 1:
1. catalyst cupport: at first get the CMK-3 of 1g drying, vacuumize the Na that infiltrates 0.1mol/L
2SO
4The aqueous solution immerses the KMnO of 0.1mol/L then in room temperature
4With Na
2SO
410min among the aqueous solution 50ml is with a large amount of distilled water washings, N
2The following 50 ℃ of dryings of atmosphere at 50 ℃ of dry 12h of vacuum, obtain load MnO again
2CMK-3 (MnO
2CMK-3) first carrier; The acetylene black that other gets the 1g drying immerses 20%HNO
324h does oleophobic property and handles, and is washed with distilled water to neutrality, as second carrier.
2. two carriers are compound: with first carrier and second carrier 1: 1 ratio by weight, grind form slurry with Kynoar (PVDF) by weight ratio mechanical ball in N-methyl pyrrolidone (NMP) medium of 45: 45: 10, it is online and carry out drying to coat collector Ni, makes electrode film thus as positive pole.Battery assembling, test condition are all with Comparative Examples 1.Test result sees the following form 1.Data from table 1 compare ratio 1 as can be seen, and the discharge performance of novel pair of carrier structure air electrode has had large increase, and catalyst is identical, but specific capacity obviously increases first.
Embodiment 2:
1. catalyst cupport: at first get the CMK-3 of 1g drying, by with embodiment 1 in 1. identical treatment conditions, obtain MnO
2CMK-3 first carrier; Other gets the oleophobic property conducting polymer polyaniline of 1g drying as second carrier.
2. two carriers are compound: with first carrier and second carrier 1: 1 ratio by weight, with among the embodiment 1 2. identical treatment conditions obtain positive pole.Battery assembling, test condition are all with Comparative Examples 1.Test result sees the following form 1.Data from table 1 compare ratio 1 and embodiment 1 as can be seen, and the discharge performance of novel pair of carrier structure air electrode has had large increase, and catalyst is identical, but specific capacity obviously increases first.
Embodiment 3:
1. catalyst cupport: get the nanotube-shaped polypyrrole of 1g, with PtCl
4The aqueous solution stirs into even suspension-turbid liquid at 80 ℃ of lower magnetic forces, dropwise adds sodium formate then.Continue to stir suspension-turbid liquid 24h, obtain catalyst Pt particle in-situ load polypyrrole nanotube, filter, washing, 80 ℃ of dry 24h down, the in-situ chemical reaction deposition obtains Pt polypyrrole first carrier; Other gets the oleophobic property conducting polymer polyaniline of 1g drying as second carrier.
2. two carriers are compound: with first carrier and second carrier 1: 1 ratio by weight, grind form slurry with Kynoar (PVDF) by weight ratio mechanical ball in N-methyl pyrrolidone (NMP) medium of 45: 45: 10, it is online and carry out drying to coat collector Ni, makes the lithium-air battery cathode film thus.
Embodiment 4:
1. catalyst cupport: the Co (NO that at first the ordered mesopore carbon CMK-3 room temperature of 1g drying is immersed 4.6mol/L
3)
2In the 50ml ethanolic solution, magnetic agitation 30min, then in 2950r/min centrifugation 30min, vacuum drying at room temperature 24h handles 4h then under 573K, and infusion process obtains Co
3O
4CMK-3 first carrier; The acetylene black that other gets the 1g drying immerses 20%HNO
324h does oleophobic property and handles, and is washed with distilled water to neutrality, as second carrier.
2. two carriers are compound: with first carrier and second carrier 1: 1 ratio by weight, grind form slurry with Kynoar (PVDF) by weight ratio mechanical ball in N-methyl pyrrolidone (NMP) medium of 45: 45: 10, it is online and carry out drying to coat collector Ni, makes the lithium-air battery cathode film thus.
Embodiment 5:
1. catalyst cupport: aniline monomer adds the 1M HCl aqueous solution to, adds catalyst perovskite knot La then
0.6Sr
0.4Fe
0.6Mn
0.4O
3(LSFM) powder (mol ratio: aniline/La
0.6Sr
0.4Fe
0.6Mn
0.4O
3=1/3), magnetic agitation 1h, ultrasonic dispersion 1h dropwise adds the 1M HCl aqueous solution of the ammonium persulfate of metering ratio then, continues to react 5h under magnetic agitation, and is centrifugal, washing, and then under 333K vacuumize 4h, obtain LSFM polyaniline first carrier; Other gets the carbon nano-tube of 1g drying and does the oleophobic property processing, as second carrier.
2. two carriers are compound: with first carrier and second carrier 1: 1 ratio by weight, grind form slurry with Kynoar (PVDF) by weight ratio mechanical ball in N-methyl pyrrolidone (NMP) medium of 45: 45: 10, it is online and carry out drying to coat collector Ni, makes the lithium-air battery cathode film thus.
Embodiment 6:
1. catalyst cupport: be work electrode with the carbon cloth, the Pt sheet is to electrode, and saturated calomel electrode (SCE) is reference electrode, 0.5M H
2SO
4, 0.5M aniline and 0.5M MnSO
42H
2O is electrolyte, cyclic voltammetric-0.2V and 1.35V (vs.SCE) 200mV s
-1Electrolysis 70s cleans, 90 ℃ of following dry 36h.Obtain MnO
2Polyaniline nano-line first carrier; Other gets dry polyaniline nano-line, as second carrier.
2. two carriers are compound: with first carrier and second carrier 1: 1 ratio by weight, grind form slurry with Kynoar (PVDF) by weight ratio mechanical ball in N-methyl pyrrolidone (NMP) medium of 45: 45: 10, it is online and carry out drying to coat collector Ni, makes the lithium-air battery cathode film thus.
Embodiment 7:
1. catalyst cupport: get 6mg multi-walled carbon nano-tubes (MWNT), 0.46ml 0.1M K
2PtCl
4Ultrasonic being scattered in the 40ml deionized water.Dropwise add 4ml formic acid then, at 80 ℃ of following backflow 30min, centrifugation, washing, 60 ℃ of following vacuumize 24h obtain PtMWNT first carrier; Other gets the oleophobic property conducting polymer polyaniline of 1g drying as second carrier.
2. two carriers are compound: with first carrier and second carrier 1: 1 ratio by weight, grind form slurry with Kynoar (PVDF) by weight ratio mechanical ball in N-methyl pyrrolidone (NMP) medium of 45: 45: 10, it is online and carry out drying to coat collector Ni, makes the lithium-air battery cathode film thus.
Table 1
Listed data as can be seen from table 1, novel pair of prepared carrier structure air electrode, because the passage that oleophobic property second carrier of no product deposition forms can be transported to oxygen each zone of air electrode, thereby the capacitance loss that can reduce the product partial occlusion to a certain extent and cause, the result has all obtained higher specific discharge capacity than Comparative Examples; And because the second carrier polyaniline among the embodiment 2 has better oleophobic property than acetylene black among the embodiment 1, more be used in oxygen conveying therein, obtained higher specific discharge capacity.As shown in Figure 2.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned instruction content of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (12)
1. two compound lithium-air battery air electrode composition of carrier, it comprises, in the total weight of described composition:
First carrier of 10-40 weight portion, its area load has the catalyst of 5-30 weight portion;
Second carrier of 10-40 weight portion, it has carried out the oleophobic property processing; And
The 5-20 parts by weight of adhesive;
Wherein, described first carrier and second carrier are identical or different, are selected from: material with carbon element, organic high molecular polymer, elemental metals and their combination.
2. composition as claimed in claim 1 is characterized in that, described material with carbon element is selected from: acetylene black, active carbon, foamy carbon, ordered mesopore carbon, carbon nano-tube and carbon nano-fiber; Described organic high molecular polymer is selected from: polyaniline, poly-propylamine, polypyrrole, polythiophene, polyacetylene and their derivative; Described elemental metals is selected from: Ni, Al and Ti.
3. composition as claimed in claim 1 is characterized in that, described catalyst is selected from: single metal oxide, composite oxide of metal, the metal simple-substance with electrochemical catalysis hydrogen reduction and oxidation activity and their combination.
4. composition as claimed in claim 3 is characterized in that, described single metal oxide is selected from: Co
3O
4, MnO
2, Mn
2O
3, CoO, ZnO, V
2O
5, MoO, Cr
2O
3, Fe
3O
4, Fe
2O
3, FeO, CuO and NiO; Described composite oxide of metal is selected from: spinel-type composite oxide of metal, pyrochlore-type composite oxide of metal and perovskite type metal composite oxides; Described metal simple-substance with electrochemical catalysis hydrogen reduction and oxidation activity is selected from: Pt, Au, Ag, Au, Co, Zn, V, Cr, Pd, Rh, Cd, Nb, Mo, Ir, Os, Ru, Ni and their combination.
5. composition as claimed in claim 1 is characterized in that, described binding agent is selected from: polytetrafluoroethylene, Kynoar, polyethylene, polyethylene glycol oxide, polyacrylonitrile and their copolymer.
6. as each described composition among the claim 1-5, it is characterized in that described first carrier and second carrier are of a size of 50-1000nm, the aperture size that described first carrier and second carrier form is 5-100nm.
7. two compound lithium-air battery air electrode preparation of compositions method of carrier, this method comprise, in the total weight of described composition:
Provide first carrier of 10-40 weight portion, at the catalyst of its area load 5-30 weight portion;
Second carrier of 10-40 weight portion is provided, it is carried out oleophobic property handle; And
The first treated carrier and second carrier are evenly mixed with the 5-20 parts by weight of adhesive by 5/1 to 1/10 weight ratio, obtain two compound lithium-air battery air electrode compositions of carrier,
Wherein, described first carrier and second carrier are identical or different, are selected from: material with carbon element, organic high molecular polymer, elemental metals and their combination.
8. method as claimed in claim 7 is characterized in that, the mode of loading of described catalyst is selected from: carrier surface in-situ chemical reaction deposition, infusion process, electroplating deposition and physical vapor deposition.
9. as claim 7 or 8 described methods, it is characterized in that described catalyst cupport thickness is 0.5-50nm.
10. method as claimed in claim 7 is characterized in that, described oleophobic property is handled and is selected from: acid treatment, water treatment and polarity are handled.
11. a lithium-air battery is with anodal, it comprises the compound lithium-air battery air electrode composition of each described pair of carrier among the claim 1-6.
12. a lithium-air battery, it comprises the described lithium-air battery of claim 11 and uses anodal as air electrode.
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| CN2010102694822A CN102214827B (en) | 2010-08-31 | 2010-08-31 | Air electrode composite of dual-carrier recombination lithium air battery and preparation method thereof |
| PCT/CN2011/079145 WO2012028095A1 (en) | 2010-08-31 | 2011-08-31 | Dual support composite air electrode composition for lithium air battery and process for preparing same |
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| CN103280586B (en) * | 2013-03-06 | 2016-12-28 | 广东工业大学 | A kind of high-energy-density lithium-air battery air electrode and battery and preparation method |
| CN103199321A (en) * | 2013-04-08 | 2013-07-10 | 中国科学院长春应用化学研究所 | Lithium air cell positive electrode material and preparation method of material |
| CN104466203B (en) * | 2013-09-22 | 2017-05-03 | 中国科学院上海硅酸盐研究所 | Composite catalyst of air electrode of lithium-air cell |
| CN104466202B (en) * | 2014-12-16 | 2016-11-30 | 北京化工大学常州先进材料研究院 | Prepared by the nickel oxide nano porous lithium O for cathode of air battery material of the supported active metals of a kind of Fluorin doped |
| CN105449226A (en) * | 2015-11-18 | 2016-03-30 | 广西师范大学 | Novel three-dimensional electrode material for lithium air battery and preparation method for novel three-dimensional electrode material |
| JP6763965B2 (en) | 2015-12-21 | 2020-09-30 | ジョンソン・アイピー・ホールディング・エルエルシー | Solid-state batteries, separators, electrodes and manufacturing methods |
| US10218044B2 (en) | 2016-01-22 | 2019-02-26 | Johnson Ip Holding, Llc | Johnson lithium oxygen electrochemical engine |
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| CN101401237A (en) * | 2006-03-14 | 2009-04-01 | 株式会社科特拉 | Fuel cell electrode catalyst with improved noble metal utilization efficiency, method for manufacturing the same, and solid polymer fuel cell comprising the same |
| CN101267057A (en) * | 2008-05-08 | 2008-09-17 | 复旦大学 | High ratio energy chargeable full-solid lithium air battery |
| CN101752628A (en) * | 2010-01-21 | 2010-06-23 | 浙江大学 | Rechargeable metal hydride air cell |
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