CN103474723A - Lithium-air battery and preparation method thereof - Google Patents
Lithium-air battery and preparation method thereof Download PDFInfo
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- CN103474723A CN103474723A CN2013104186429A CN201310418642A CN103474723A CN 103474723 A CN103474723 A CN 103474723A CN 2013104186429 A CN2013104186429 A CN 2013104186429A CN 201310418642 A CN201310418642 A CN 201310418642A CN 103474723 A CN103474723 A CN 103474723A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
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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
- Y02E60/10—Energy storage using batteries
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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 lithium-air battery which comprises an anode, a cathode and an electrolyte system, wherein the anode comprises a porous hydrophobic carbon paper current collector and a coating layer on the porous hydrophobic carbon paper current collector; the cathode refers to lithium metal; the electrolyte system refers to sulfolane and lithium salt. The sulfolane has a relatively high electric medium constant and relatively high chemical stability; an electrochemical window of sulfolane-based electrolyte is wide and relatively good in ionic conductivity and stability and can be combined with the porous conductive carbon paper current collector specifically; the prepared lithium-air battery has the very excellent cycle performance. Under the condition that the charge and discharge capacity of the battery is kept in 1000mAh/g, and the voltage of the battery is 2.2-5.0V, the open-circuit voltage of the battery is 3V, and the battery can be cycled for thousands of times. The invention also provides a preparation method of the lithium-air battery.
Description
Technical field
The present invention relates to the electrochemical energy source domain, relate in particular to a kind of lithium-air battery and preparation method thereof.
Background technology
Lithium-air battery is a kind of very high-energy battery of high-energy-density that has, and with common anode material for lithium-ion batteries, compares, and the positive active material of lithium-air battery is airborne oxygen, inexhaustible.In the situation that anode is excessive, the termination of electric discharge is to stop up the air electrode duct by discharging product to be controlled.In practical application, oxygen is provided by external environment, so the lithium-air battery energy density exceeds 1-2 the order of magnitude than existing lithium battery system.In addition, lithium-air battery is a kind of eco-friendly novel battery system, can be for clean battery power will be provided future.Comprehensive its cheap, safety and environmental protection, the advantage of the each side such as specific energy height, once the Reversible Cycle of lithium-air battery is really set up, the development of the metal-air cells such as lithium-air battery in fields such as electrical network energy storage, electric automobile, Aero-Space will be promoted greatly.This not only can bring revolutionary technological break-through to battery industry, also will become a milestone of whole metal-air cell.
The research of relevant lithium-air battery both at home and abroad is very active, and it is reasonably constructed and there is no final conclusion.In order to set up the real Reversible Cycle of lithium-air battery, must possess stable electrolyte system, suitable plus plate current-collecting body, and the painting membrane substance that can improve the battery charging and discharging performance.As, the patent documentation of application number 201310120005.3 discloses sulfone class electrolyte for a kind of lithium-air battery, described sulfone class electrolyte has low volatility, high dissolved oxygen ability, electrochemical window is wide, especially super oxygen root is had to excellent stability, but be conducive to the inhibition of reversion products generation and side reaction.And in the document, do not adopt suitable air positive pole, prepared lithium-air battery that 5 circulations are only arranged.Usually take aluminium net, nickel foam, porous ceramics piece in prior art is the anodal matrix of air, and organic carbonate class or ethers are electrolyte, and cycle-index generally also only has more than 100 time.
Summary of the invention
The object of the present invention is to provide a kind of lithium-air battery, described lithium-air battery has good cycle performance, to solve the poor problem of current lithium-air battery cycle performance.
The present invention realizes that the technical scheme of above-mentioned purpose is: a kind of lithium-air battery, comprise positive pole, and negative pole and electrolyte, described positive pole comprises the carbon paper collector; Described electrolyte comprises sulfolane and lithium salts.
Further, described lithium salts is two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI), lithium hexafluoro phosphate (LiPF
6), dioxalic acid lithium borate (LiBOB), LiBF4 (LiBF
4) at least one.
Further, described electrolyte also comprises dimethyl sulfoxide (DMSO) and/or tetraethylene glycol dimethyl ether.
Further, in described electrolyte, the molar concentration of lithium salts is 0.5～5mol/L.
Further, described carbon paper collector is that at least one mask has hydrophobic carbon fiber paper.
Further, described positive pole also comprises the coat on the carbon paper collector, and described coat comprises carbon, lithium peroxide and polytetrafluoroethylene, and the quality of described polytetrafluoroethylene is 5%～10% of coat quality; The quality of described lithium peroxide is 5%～60% of carbon and lithium peroxide quality summation.
The present invention also provides a kind of preparation method of lithium-air battery, comprises the steps:
A. the configuration of electrolyte solution
Lithium salts is mixed with sulfolane, make electrolyte solution, wherein, the concentration of described lithium salts is 0.5-5mol/L;
B. anodal making
(1) porous, electrically conductive carbon and lithium peroxide are mixed, mix with polytetrafluoroethylene after grinding, obtain mixed liquor; (2) described mixed liquor is joined in 1-METHYLPYRROLIDONE, stir under 40-80 ℃, obtain mixed slurry; (3) described mixed slurry is filmed on the carbon paper collector, dry, obtain anodal;
C. the making of negative pole
The lithium metal is negative pole;
D. by described electrolyte solution, positive pole, negative pole, in inert gas atmosphere, encapsulation obtains described lithium-air battery.
Further, electrolyte solution described in steps A also comprises dimethyl sulfoxide (DMSO) and/or tetraethylene glycol dimethyl ether.
Further, lithium salts described in steps A is LiTFSI, LiPF
6, LiBOB, LiBF
4in at least one.
Further, described carbon paper collector is that at least one mask has hydrophobic carbon fiber paper.
Further, the quality of polytetrafluoroethylene described in step B is 5%～10% of mixed liquor quality; The quality of described lithium peroxide is 5%～60% of carbon and lithium peroxide quality summation.
Further, described in step B, the volume of 1-METHYLPYRROLIDONE is mixeding liquid volume 3～5 times.
Further, encapsulation described in step D also comprises barrier film, battery case, pad, shell fragment, the order of described encapsulation, from the negative pole to the positive pole, is negative battery shell, shell fragment, pad, lithium metal, electrolyte, barrier film, electrolyte, positive pole, positive battery shell successively.
Further, the controlled pressure encapsulated in described step D is 45-50Mpa, and in packaging environment, the content of water and oxygen all is less than 0.5ppm.
Beneficial effect of the present invention is:
(1) good cycle performance.Lithium-air battery of the present invention is that under 1000mAh/g, the voltage range situation that is 2.2-5.0V, cycle-index all can reach more than 1000 times, has very superior cycle performance, reaches as high as 1100 circulations keeping charging and discharging capacity.
(2) specific capacity conservation rate, energy efficiency are high.Battery of the present invention has 100% specific capacity conservation rate, and primary power efficiency can reach 85% left and right.Even after circulation 1100 times, still there is 100% specific capacity conservation rate, average energy efficiency also can remain on 69%.
(3) effectively control anodal corrosion phenomenon.Common carbon paper or metal collector (nickel screen, pinch foam, aluminium foil etc.) material has corrosion phenomenon in charging voltage higher than ubiquity after 4.2V, and the present invention selects hydrophobic carbon paper as collector, has effectively controlled the generation of anodal corrosion phenomenon.
In a word, the electrolyte system of sulfolane and lithium salts, the lithium-air battery prepared of being combined with the positive pole that is coated with porous carbon-lithium peroxide is the lithium-air battery of a brand-new system, it is also the combination of best results so far, keeping charging and discharging capacity, be under 1000mAh/g, the voltage range situation that is 2.2-5.0V, cycle-index can reach 1100 times more than, is under equal conditions to obtain in the world the highest cycle-index at present.
The accompanying drawing explanation
Fig. 1 is lithium-air battery model of the present invention.
Fig. 2 is containing LiTFSI lithium-air battery specific capacity-voltage curve.
Fig. 3 is containing LiPF
6lithium-air battery specific capacity-voltage curve.
Fig. 4 is containing LiBOB lithium-air battery specific capacity-voltage curve.
Fig. 5 is containing LiBF
4lithium-air battery specific capacity-voltage curve.
Fig. 6 is the specific capacity-voltage curve of the embodiment of the present invention 1 lithium-air battery.
Fig. 7 is the capacity-voltage curve of the anodal lithium battery of nickel foam.
Fig. 8 is the capacity-voltage curve of the hydrophobic carbon paper lithium battery of single face.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Specific embodiment described herein only, in order to explain the present invention, does not limit the present invention.
It is excellent that the present invention works out a kind of chemical property by the multiple improvement to battery material, and security performance is good, has the lithium-air battery of remarkable cycle characteristics.In the situation that keep charging and discharging capacity, be that 1000mAh/g, voltage range are 2.2-5.0V, the cycle-index that the present invention obtains reaches as high as more than 1100 times.
The present invention comprises the multiple improvement of battery material:
The electrolyte aspect, the present invention in conjunction with the sulfolane electrolyte solvent can anti-high voltage, the advantage such as high, the stable chemical nature of electric medium constant, select sulfolane as electrolyte solvent, separately can add other solvents, as dimethyl sulfoxide (DMSO) (DMSO) and or tetraethylene glycol dimethyl ether (TEGDME) etc. mixed and modified.The electrolyte melting point depression of tetraethylene glycol dimethyl ether modification, make electrolyte be adapted to use under lower temperature conditions; Dimethyl sulfoxide (DMSO) makes the lithium-air battery charging voltage lower as electrolysis additive.
The electrolyte lithium salt aspect, the present invention has adopted LiTFSI, LiPF
6, LiBOB, LiBF
4in at least one electrolyte lithium salt as lithium-air battery, make lithium-air battery reach higher cycle life.When especially lithium salt suitably increases in electrolyte, or, when mixture that lithium salts is two or more, can improve electrolyte intermediate ion conductivity, improve stability test, make the circulation of lithium-air battery efficient stable.
The collector aspect, the carbon paper collector can be any one in carbon fiber, graphite foil, carbon cloth, preferably carbon fiber paper collector.The present invention has adopted at least one mask that the carbon paper collector of hydrophobic performance is arranged, wherein a kind of carbon paper collector is that single face is hydrophobic, another side is conductive layer, so both can better separate steam, to prevent the infringement of water steam to lithium-air battery, can provide afflux effect preferably again, impel lithium-air battery that higher performance is arranged.Another kind of carbon paper collector all has hydrophobic layer in two sides, and so better the isolated water steam, higher from practical angle fail safe.
The positive electrode aspect, in order further to improve the performance of battery, be covered with a coating film at the carbon paper collection liquid surface, and described filming comprises porous, electrically conductive carbon, lithium peroxide and polytetrafluoroethylene (PTFE).Wherein the quality of polytetrafluoroethylene is 5%～10% of coat quality, and the polytetrafluoroethylene stable in properties, make binding agent, can hold preferably positive active material; Carbon and lithium peroxide can be arbitrarily than mixing, 5%～60% of the quality summation that preferably quality of lithium peroxide is carbon and lithium peroxide, appropriate lithium peroxide is as discharging product and active material, can effectively promote the crystallization of discharging product, and the deficiency that makes up active material while charging, reach and promote to discharge and recharge the purpose that reaction is carried out smoothly; Porous, electrically conductive carbon can not only promote anodal electrical conductivity, and has reasonable aperture, and effectively the controlled discharge product stops up the air positive pole.The conductivity range of pole piece be 108.92s/cm to 147.10s/cm, the battery open circuit voltage obtained is in about 3.0V.
The present invention is in conjunction with above-mentioned each individual system, the lithium-air battery that has obtained having the excellent cycle performance.This battery be take lithium metal as negative pole, and sulfolane and lithium salts are electrolyte system, just very is coated with the hydrophobic carbon paper of carbon, lithium peroxide, polytetrafluoroethylene coat.
The preparation method that the present invention has the lithium-air battery of excellent cycling performance comprises the steps:
A. the configuration of electrolyte solution
Lithium salts is mixed with sulfolane, make electrolyte solution, wherein, the concentration of described lithium salts is 0.5-5mol/L;
B. anodal making
(1) porous, electrically conductive carbon and lithium peroxide are mixed, mix with polytetrafluoroethylene after grinding, obtain mixture; (2) described mixture is joined in 1-METHYLPYRROLIDONE, stir under 40～80 ℃, obtain mixed slurry; (3) described mixed slurry is filmed on the carbon paper collector, dry, obtain anodal;
C. the making of negative pole
The lithium metal is negative pole;
D. by described electrolyte solution, positive pole, negative pole, in inert gas atmosphere, encapsulation obtains described lithium-air battery.
Below by a plurality of embodiment, the present invention is described further:
A. the preparation of electrolyte solution
Take the LiTFSI of 0.1mol, measure the liquid sulfolane solvent of 0.1L, be less than at water content under the environmental condition of 0.5ppm, lithium salts is slowly added in sulfolane solvent, fully stir and within 1 hour, be mixed with the even electrolyte solution that concentration is 1mol/L.The content of electrolytical free acid and water all requires to be less than 10ppm.
B. anodal preparation
At first, measure 4.05g porous, electrically conductive carbon, the 4.95g lithium peroxide, adopt agate mortar hand lapping or ball mill automatic grinding, obtains porous, electrically conductive carbon and lithium peroxide homogeneous mixture.Said mixture is joined in the 1g polytetrafluoroethylene (PTFE) and forms mixture.Said mixture is joined in 20g methyl pyrrolidone (NMP) dispersant, in the magnetic force heating stirrer, with 40～80 ℃ of temperature blend 4 hours, form the thickness suspension that comprises whole anodal class coating materials.Thickness suspension is evenly spread to a side of the dry carbon paper that is placed in evacuated panel, use the high wind heating and, under the promotion of automatic spray dryer, with the speed of per second 10～15mm, carry out uniform coating, obtain with glossiness, moistening positive plate.Finally put it in drying box and under 60-80 ℃ of temperature conditions, methyl pyrrolidone (NMP) is dried 3 hours, obtain the target positive plate.
C. take lithium metal as negative pole
D. ready electrolyte solution, positive plate, lithium an-ode in steps A, B, C, in the content of water and oxygen all is less than the totally-enclosed glove box of 0.5ppm, are assembled into to lithium-air battery; The order of encapsulation, from the negative pole to the positive pole, is negative battery shell, shell fragment, pad, lithium metal, electrolyte, barrier film, electrolyte, positive pole, positive battery shell successively; By the lithium-air battery integrated moving that assembles, to the mould indent of hand press, controlled pressure is that 45～50Mpa compresses battery, after 30 seconds, it is taken off and can obtain described lithium-air battery.
Embodiment 2
Other conditions are with embodiment 1, the LiPF that only to change the lithium salts that uses in the electrolyte solution preparation be 0.1mol
6.
Embodiment 3
Other conditions are with embodiment 1, the LiBOB that only to change the lithium salts that uses in the electrolyte solution preparation be 0.1mol.
Other conditions are with embodiment 1, the LiBF that only to change the lithium salts that uses in the electrolyte solution preparation be 0.1mol
4.
[experimental example 1] is containing the lithium-air battery cycle performance test of different lithium salts
Get the embodiment of the present invention 1,2,3,4 prepared lithium-air batteries, the control current density is 0.05mA/cm
2, specific capacity is 1000mAh/g, records and discharges and recharges specific discharge capacity and change in voltage curve as shown in accompanying drawing 2,3,4,5.All batteries are all capable of circulation more than 150 times, and the prepared lithium-air battery of the present invention has good cycle performance.Comparative drawings figs is known, in general, and best results when lithium salts is chosen as LiTFSI.
[experimental example 2] electrochemical property test
With the prepared lithium-air battery of the embodiment of the present invention 1, controlling measuring current density is 0.05mA/cm2, and specific capacity is 1000mAh/g, records the specific capacity-voltage curve of battery as shown in Figure 6.As seen from the figure, this lithium-air battery is 2.2 in the voltage range of 5.0V, and the maintenance specific capacity is 1000mAh/g, can realize 1100 circulations, possesses very good cycle performance.
[experimental example 3] different plus plate current-collecting body material contrast
Other conditions, with embodiment 1, only change the plus plate current-collecting body material, with nickel foam, replace single face hydrophobic carbon standby lithium-air battery made of paper.Under the 0.088mA condition, charge/discharge capacity is 0.1mAh, and the lithium-air battery capacity that the nickel foam recorded is positive electrode-voltage charge and discharge cycles curve as shown in Figure 7; The battery capacity that carbon paper is positive electrode-voltage charge and discharge cycles curve as shown in Figure 8.As can be seen from the figure, the present invention selects carbon paper make collector and reveal more stable chemical property containing the electrolyte combination table of sulfolane specifically.
Claims (14)
1. a lithium-air battery, comprise positive pole, and negative pole and electrolyte, is characterized in that, described positive pole comprises the carbon paper collector; Described electrolyte comprises sulfolane and lithium salts.
2. a kind of lithium-air battery according to claim 1, is characterized in that, described lithium salts is LiTFSI, LiPF
6, LiBOB, LiBF
4in at least one.
3. a kind of lithium-air battery according to claim 1, is characterized in that, described electrolyte also comprises dimethyl sulfoxide (DMSO) and/or tetraethylene glycol dimethyl ether.
4. a kind of lithium-air battery according to claim 1 and 2, is characterized in that, in described electrolyte, the molar concentration of lithium salts is 0.5～5mol/L.
5. a kind of lithium-air battery according to claim 1, is characterized in that, described carbon paper collector is that at least one mask has hydrophobic carbon fiber paper.
6. a kind of lithium-air battery according to claim 1, is characterized in that, described carbon paper collector comprises one deck coat, and described coat comprises carbon, lithium peroxide and polytetrafluoroethylene, and the quality of described polytetrafluoroethylene is 5%～10% of coat quality; The quality of described lithium peroxide is 5%～60% of carbon and lithium peroxide quality summation.
7. the preparation method of a lithium-air battery, is characterized in that, comprises the steps:
A. the configuration of electrolyte solution
Lithium salts is mixed with sulfolane, make electrolyte solution, wherein, the concentration of described lithium salts is 0.5-5mol/L;
B. anodal making
(1) porous, electrically conductive carbon and lithium peroxide are mixed, mix with polytetrafluoroethylene after grinding, obtain mixed liquor; (2) described mixture is joined in 1-METHYLPYRROLIDONE, stir under 40-80 ℃, obtain mixed slurry; (3) described mixed slurry is filmed on the carbon paper collector, dry, obtain anodal;
C. the making of negative pole
The lithium metal is negative pole;
D. by described electrolyte solution, positive pole, negative pole, in inert gas atmosphere, encapsulation obtains described lithium-air battery.
8. preparation method according to claim 7, is characterized in that, electrolyte solution described in steps A also comprises dimethyl sulfoxide (DMSO) and/or tetraethylene glycol dimethyl ether.
9. preparation method according to claim 7, is characterized in that, lithium salts described in steps A is LiTFSI, LiPF
6, LiBOB, LiBF
4in at least one.
10. preparation method according to claim 7, is characterized in that, described carbon paper collector is that at least one mask has hydrophobic carbon fiber paper.
11. preparation method according to claim 7, is characterized in that, the quality of polytetrafluoroethylene described in step B is 5%～10% of mixed liquor quality; The quality of described lithium peroxide is 5%～60% of carbon and lithium peroxide quality summation.
12. preparation method according to claim 7, is characterized in that, the volume of 1-METHYLPYRROLIDONE described in step B is mixeding liquid volume 3～5 times.
13. preparation method according to claim 7, is characterized in that, the order encapsulated described in step D, from the negative pole to the positive pole, is negative battery shell, shell fragment, pad, lithium metal, electrolyte, barrier film, electrolyte, positive pole, positive battery shell successively.
14. preparation method according to claim 7, is characterized in that, the controlled pressure encapsulated in described step D is 45-50Mpa, and in packaging environment, the content of water and oxygen all is less than 0.5ppm.
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| PCT/CN2013/085682 WO2015035683A1 (en) | 2013-09-13 | 2013-10-22 | Lithium-air battery and manufacturing method therefor |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101861676A (en) * | 2009-01-16 | 2010-10-13 | 丰田自动车株式会社 | Air secondary battery and method for manufacturing the same |
| CN102227035A (en) * | 2011-05-16 | 2011-10-26 | 清华大学 | Lithium-air battery with double-layer controllable anode structure |
| CN102263311A (en) * | 2011-06-27 | 2011-11-30 | 清华大学 | Bipolar-structured lithium-air battery |
| CN102948006A (en) * | 2010-04-27 | 2013-02-27 | 汉阳大学校产学协力团 | Lithium-air battery |
| CN103208668A (en) * | 2013-04-08 | 2013-07-17 | 中国科学院长春应用化学研究所 | Sulfone electrolyte for lithium-air battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544522A (en) * | 2012-01-11 | 2012-07-04 | 复旦大学 | Composite air electrode of lithium air cell and preparation method thereof |
-
2013
- 2013-09-13 CN CN2013104186429A patent/CN103474723A/en active Pending
- 2013-10-22 WO PCT/CN2013/085682 patent/WO2015035683A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101861676A (en) * | 2009-01-16 | 2010-10-13 | 丰田自动车株式会社 | Air secondary battery and method for manufacturing the same |
| CN102948006A (en) * | 2010-04-27 | 2013-02-27 | 汉阳大学校产学协力团 | Lithium-air battery |
| CN102227035A (en) * | 2011-05-16 | 2011-10-26 | 清华大学 | Lithium-air battery with double-layer controllable anode structure |
| CN102263311A (en) * | 2011-06-27 | 2011-11-30 | 清华大学 | Bipolar-structured lithium-air battery |
| CN103208668A (en) * | 2013-04-08 | 2013-07-17 | 中国科学院长春应用化学研究所 | Sulfone electrolyte for lithium-air battery |
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