CN109428138A - The preparation method and lithium-air battery of lithium-air battery - Google Patents
The preparation method and lithium-air battery of lithium-air battery Download PDFInfo
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- CN109428138A CN109428138A CN201710736352.7A CN201710736352A CN109428138A CN 109428138 A CN109428138 A CN 109428138A CN 201710736352 A CN201710736352 A CN 201710736352A CN 109428138 A CN109428138 A CN 109428138A
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- lithium
- air battery
- preparation
- anode
- battery
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000006258 conductive agent Substances 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000010405 anode material Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011863 silicon-based powder Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 17
- 238000007599 discharging Methods 0.000 abstract description 9
- 229910000676 Si alloy Inorganic materials 0.000 abstract description 8
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 abstract 3
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000002041 carbon nanotube Substances 0.000 description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 description 7
- 230000005611 electricity Effects 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000002210 silicon-based material Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229910021487 silica fume Inorganic materials 0.000 description 3
- -1 Super P Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 101100373011 Drosophila melanogaster wapl gene Proteins 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- ZSYNKHJUSDFTCQ-UHFFFAOYSA-N [Li].[Fe].P(O)(O)(O)=O Chemical group [Li].[Fe].P(O)(O)(O)=O ZSYNKHJUSDFTCQ-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000004483 pasc Anatomy 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Classifications
-
- 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
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
Abstract
The present invention provides a kind of lithium-air battery preparation methods of no lithium metal, comprising: (1) mixes silicon based anode material, conductive agent, binder and be coated on negative current collector；(2) in anhydrous and oxygen-free environment, catalyst, conductive agent, binder, lithium nitride is mixed and are pressed onto plus plate current-collecting body；(3) in anhydrous and oxygen-free environment, positive and negative anodes are separated with diaphragm, electrolyte is added dropwise, is assembled into lithium-air battery.The present invention uses lithium nitride as lithium source, and silica-base material forms Li-Si alloy cathode in first circle charging as cathode, instead of lithium metal, avoids the generation of Li dendrite, and the vacancy that lithium nitride decomposition generates can effectively store discharging product lithium peroxide.
Description
Technical field
The present invention relates to a kind of preparation methods of lithium-air battery, belong to field of fuel cell technology.
Background technique
Increase with modern society to energy demand urgency, the secondary cell of high-energy density have become the following energy
The emphasis of source industry development, lithium ion battery is become with its performance advantage outstanding applies secondary cell the most universal.However,
The existing common negative electrode material of lithium ion battery is graphitized charcoal, and theoretical specific capacity 370mAh/g, positive electrode is phosphoric acid
Iron lithium, cobalt acid lithium, LiMn2O4, ternary material, actual specific capacity is far from meeting the needs of modern society.Especially electronic vapour
The rapid development of vehicle proposes requirements at the higher level for the development of energy-density lithium ion battery.The height of metallic lithium base battery system
Specific energy advantage is more and more to be become the focus of people's research and developing direction, such as lithium-sulfur cell and lithium-air cell, Li/S
The theoretical energy density of battery can be up to 2600Wh/Kg, and the energy density of lithium-air battery is more up to 3500Wh/Kg, far
Much higher than the energy density of current traditional lithium-ion battery about 200Wh/Kg.But use lithium metal as secondary battery negative pole material
It is main that material has two, first is that easily occurring with electrolyte in cyclic process can not due to the high activity of lithium metal
Back reaction consumes electrolyte, causes coulombic efficiency to reduce, and lead to ultimate failure；Second is that lithium metal formation in cyclic process
Dendrite and " dead lithium " can also reduce the cycle efficieny of lithium electrode, if Li dendrite continued propagation can pierce through diaphragm and lead to short circuit even
A series of safety problems such as explosion.Particularly, since lithium-air battery is Semi-open system, the protection for lithium metal is one
Stubborn problem.Therefore the height ratio capacity negative electrode material for finding a kind of alternative lithium metal is of great significance.
Silicon materials have the theoretical specific capacity of up to 4200mAh/g, have lower charge and discharge platform relative to lithium, still
To be used for lithium-air battery, it is necessary to first react it to form alloy with lithium, Li-Si alloy chemical property is active, prepare electrode compared with
Difficulty, and performance is unstable.Therefore silicon based anode material being applied to lithium-air battery, there is also very big challenges.
Summary of the invention
The object of the present invention is to provide a kind of lithium-air battery production method of no lithium metal and utilize this method production
Lithium-air battery, wherein avoiding existing for lithium metal that coulombic efficiency is low, safety is low, lithium as cathode using silica-base material
Dendrite problems.The lithium-air battery uses lithium nitride as lithium source, and the original of silicon-based anode is realized by once assembling lithium-air battery
Position Electrochemical lithiation, and the vacancy of lithium nitride decomposition generation can effectively store the discharging product of lithium-air battery.This is without gold
The lithium-air battery preparation method of category lithium is easy to operate, is easily industrialized application.
The present invention is achieved by the following technical solutions:
In a first aspect, the present invention provides a kind of preparation methods of lithium-air battery comprising following steps:
Battery cathode and anode are prepared respectively；
In anhydrous and oxygen-free environment, successively the anode, diaphragm and anode are packaged, and electrolysis is added dropwise
Liquid obtains the lithium-air battery；
The battery cathode the preparation method comprises the following steps:
It after silicon based anode material, conductive agent and adhesive are mixed, is coated on negative current collector, is obtained after dry described
Battery cathode.
Preferably, cathode with conductive agent is one of acetylene black, Super P, Ketjen black, electrically conductive graphite or several
Kind.
Preferably, cathode is polyacrylic acid, sodium alginate, sodium carboxymethylcellulose, polyvinylidene fluoride with adhesive
One or more of alkene, cyclodextrin, Arabic gum, xanthan gum, guar gum.
Preferably, the anode the preparation method comprises the following steps:
In anhydrous and oxygen-free environment, after lithium nitride, catalyst, conductive agent and adhesive are mixed, it is pressed in plus plate current-collecting body
On, obtain anode.
Preferably, the material of the plus plate current-collecting body is nickel foam or carbon paper.
Preferably, content of the catalyst in anode is 1~10%.
Preferably, the catalyst is carbon nanotube, Pt, Ru, Pd, Ag, Au, RuO2、MnO2、 Co3O4、Fe3O4
One or more of.
Preferably, anode with conductive agent is one of acetylene black, Super P, Ketjen black, electrically conductive graphite or several
Kind.
Preferably, the binder is PTFE.
Preferably, the negative current collector is copper foil.
Preferably, the silicon based anode material is selected from nano silica fume, micron silicon powder, silicon/carbon composite, oxidation
One or more of sub- silicon, the sub- silicon/carbon composite of oxidation.
Preferably, the electrolyte includes lithium salts and solvent, and the lithium salts is selected from LiNO3、LiPF6、 LiTFSI、
LiFSI、LiClO4、LiCF3SO3One or more of, the solvent is selected from glycol dimethyl ether, diethylene glycol dimethyl ether, three
One or more of glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dimethyl sulfoxide, N,N-dimethylformamide.
It preferably, also include film for additive in the electrolyte, the film for additive is in the electrolytic solution
Mass fraction be 1~5%, the film for additive is preferably fluorinated ethylene carbonate.
Preferably, the positive electrode and anode material capacity ratio are 1.05~1.2.
In the present invention, lithium nitride generates nitrogen and lithium ion after decomposing；
Nitrogen is discharged by air electrode, and lithium ion reaches cathode by electrolyte and pasc reaction forms Li-Si alloy.
Second aspect, the present invention also provides a kind of lithium-air batteries prepared by preceding method.
Lithium nitride has the theoretical specific capacity of 2300mAh/g, under lower current potential just (relative to lithium metal 1V or so)
It can decompose, and decomposition product is lithium ion and nitrogen, since lithium-air battery is Semi-open system, the nitrogen of generation is easy to
It removes.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, use silica-base material instead of lithium metal as the negative electrode material of lithium-air battery, lithium metal is in lithium-air battery
In efficiency be 20%~30%, silica-base material has 90% or more efficiency, avoids that lithium metal bring is inefficient, low peace
Full property and dendrite problems；
2, using lithium nitride as lithium source, the disposable battery that makes forms Li-Si alloy cathode, obtains the lithium air of function admirable
Battery.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the first circle charging curve that the lithium-air battery without lithium metal is made in embodiment 1 in the present invention；
Fig. 2 is the 2nd, the 5 circle charging and discharging curves that the lithium-air battery without lithium metal is made in embodiment 1 in the present invention；
Fig. 3 is the first circle charging curve that the lithium-air battery without lithium metal is made in embodiment 3 in the present invention；
Fig. 4 is the 2nd, 5, the 10 circle charging and discharging curves that the lithium-air battery without lithium metal is made in embodiment 3 in the present invention.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
Use nano silicon material for cathode, carbon nanotube is anode catalyst, a kind of lithium-air battery system of no lithium metal
It is as follows to make method and step:
(1) nano silica fume, conductive agent, binder are mixed with slurry, are coated on copper foil, electricity is obtained after vacuum drying
Pond cathode portion；
(2) in anhydrous and oxygen-free environment, lithium nitride, carbon nanotube, conductive agent, binder is sufficiently mixed, mixture is taken
It is pressed in nickel foam, forms anode portion；
(3) in anhydrous and oxygen-free environment, successively the anode, diaphragm, cathode of above-mentioned preparation are encapsulated, and electrolyte is added dropwise.
So far, the lithium-air battery production of no lithium metal finishes.
The charging and discharging curve of the lithium-air battery of no lithium metal manufactured in the present embodiment as shown in Figure 1, lithium nitride decomposition
It is predominantly located at 1V or so, after charging to 3.5V, lithium nitride is substantially completely decomposed, real in cathode formation Li-Si alloy, the present invention
The 2nd, 5 circle charging and discharging curves of the obtained lithium-air battery without lithium metal of example 1 are applied as shown in Fig. 2, Li-Si alloy is as cathode, carbon
Nanotube is as catalyst, with capacity 0.9mAh cm in oxygen-2Carrying out charge and discharge can be with normal circulation, and the electricity that charged
Position is smaller.
Embodiment 2
Use nano silicon material for cathode, it is anode catalyst that carbon, which carries Ru catalyst, a kind of lithium air electricity of no lithium metal
Steps are as follows for pond production method:
(1) nano silica fume, conductive agent, binder are mixed with slurry, are coated on copper foil, electricity is obtained after vacuum drying
Pond cathode portion；
(2) in anhydrous and oxygen-free environment, lithium nitride, carbon are carried Ru catalyst, conductive agent, binder and is sufficiently mixed, is taken mixed
It closes object to be pressed in nickel foam, forms anode portion；
(3) in anhydrous and oxygen-free environment, successively the anode, diaphragm, cathode of above-mentioned preparation are encapsulated, and electrolyte is added dropwise.
So far, the lithium-air battery production of no lithium metal finishes.
Embodiment 3
Use the sub- silicon materials of oxidation for cathode, carbon nanotube is anode catalyst, a kind of lithium-air battery of no lithium metal
Steps are as follows for production method:
(1) sub- silicon, conductive agent, binder will be aoxidized and is mixed with slurry, be coated on copper foil, electricity is obtained after vacuum drying
Pond cathode portion；
(2) in anhydrous and oxygen-free environment, lithium nitride, carbon nanotube, conductive agent, binder is sufficiently mixed, mixture is taken
It is pressed in nickel foam, forms anode portion；
(3) in anhydrous and oxygen-free environment, successively the anode, diaphragm, cathode of above-mentioned preparation are encapsulated, and electrolyte is added dropwise.
So far, the lithium-air battery production of no lithium metal finishes.
The charging and discharging curve of the lithium-air battery of no lithium metal manufactured in the present embodiment as shown in figure 3, lithium nitride decomposition
It is predominantly located at 1V or so, after charging to 3.5V, lithium nitride is substantially completely decomposed, and in negative electrode lithium ion and aoxidizes sub- silicon formation lithium silicon
Alloy, the present invention in embodiment 3 be made the lithium-air battery without lithium metal the 2nd, 5,10 circle charging and discharging curves as shown in figure 4,
Li-Si alloy is as cathode, and carbon nanotube is as catalyst, with capacity 0.18mAh cm in oxygen-2Carrying out charge and discharge can be just
Often circulation, and the overpotential that charges is smaller.
Embodiment 4
Use the sub- silicon materials of oxidation for cathode, it is anode catalyst, a kind of lithium air of no lithium metal that carbon, which carries Ru catalyst,
Steps are as follows for battery production method:
(1) sub- silicon, conductive agent, binder will be aoxidized and is mixed with slurry, be coated on copper foil, electricity is obtained after vacuum drying
Pond cathode portion；
(2) in anhydrous and oxygen-free environment, lithium nitride, carbon are carried Ru catalyst, conductive agent, binder and is sufficiently mixed, is taken mixed
It closes object to be pressed in nickel foam, forms anode portion；
(3) in anhydrous and oxygen-free environment, successively the anode, diaphragm, cathode of above-mentioned preparation are encapsulated, and electrolyte is added dropwise.
So far, the lithium-air battery production of no lithium metal finishes.
Embodiment 5
Use the sub- silicon materials of oxidation for cathode, carbon carries RuO2Catalyst is anode catalyst, and a kind of lithium of no lithium metal is empty
Steps are as follows for gas battery production method:
(1) sub- silicon, conductive agent, binder will be aoxidized and is mixed with slurry, be coated on copper foil, electricity is obtained after vacuum drying
Pond cathode portion；
(2) in anhydrous and oxygen-free environment, lithium nitride, carbon are carried into RuO2Catalyst, conductive agent, binder are sufficiently mixed, and are taken
Mixture is pressed in nickel foam, forms anode portion；
(3) in anhydrous and oxygen-free environment, successively the anode, diaphragm, cathode of above-mentioned preparation are encapsulated, and electrolyte is added dropwise.
So far, the lithium-air battery production of no lithium metal finishes.
In conclusion being made the present invention provides a kind of lithium-air battery production method of no lithium metal and using this method
Lithium-air battery, wherein using silica-base material as cathode, avoid existing for lithium metal coulombic efficiency is low, safety is low,
Li dendrite problem.The lithium-air battery uses lithium nitride as lithium source, realizes silicon-based anode by once assembling lithium-air battery
The embedding lithium of electrochemical in-situ, and the vacancy of lithium nitride decomposition generation can effectively store the discharging product of lithium-air battery.The nothing
The lithium-air battery preparation method of lithium metal is easy to operate, is easily industrialized application.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (10)
1. a kind of preparation method of lithium-air battery, which comprises the steps of:
Battery cathode and anode are prepared respectively；
In anhydrous and oxygen-free environment, successively the anode, diaphragm and anode are packaged, and electrolyte is added dropwise,
Obtain the lithium-air battery；
The battery cathode the preparation method comprises the following steps:
It after silicon based anode material, conductive agent and adhesive are mixed, is coated on negative current collector, obtains the battery after dry
Cathode.
2. the preparation method of lithium-air battery as described in claim 1, which is characterized in that the preparation method of the anode
Are as follows:
In anhydrous and oxygen-free environment, after lithium nitride, catalyst, conductive agent and adhesive are mixed, it is pressed on plus plate current-collecting body, obtains
To anode.
3. the preparation method of lithium-air battery as claimed in claim 2, which is characterized in that the material of the plus plate current-collecting body is
Nickel foam or carbon paper.
4. the preparation method of lithium-air battery as claimed in claim 2, which is characterized in that the catalyst is in anode
Content be 1~10%.
5. the preparation method of lithium-air battery as claimed in claim 2 or 4, which is characterized in that the catalyst is carbon nanometer
Pipe, Pt, Ru, Pd, Ag, Au, RuO2、MnO2、Co3O4、Fe3O4One or more of.
6. the preparation method of lithium-air battery as claimed in claim 2, which is characterized in that the binder is PTFE.
7. the preparation method of lithium-air battery as described in claim 1, which is characterized in that the negative current collector is copper foil.
8. the preparation method of lithium-air battery as described in claim 1, which is characterized in that the silicon based anode material is selected from and receives
One or more of rice silicon powder, micron silicon powder, silicon/carbon composite, the sub- silicon of oxidation, the sub- silicon/carbon composite of oxidation.
9. the preparation method of lithium-air battery as described in claim 1, which is characterized in that the electrolyte includes lithium salts and molten
Agent, the lithium salts are selected from LiNO3、LiPF6、LiTFSI、LiFSI、LiClO4、LiCF3SO3One or more of, the solvent
Selected from glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dimethyl sulfoxide, N, N-
One or more of dimethylformamide.
10. a kind of lithium-air battery prepared by claim 1 the method.
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| CN114899348A (en) * | 2022-06-21 | 2022-08-12 | 天目湖先进储能技术研究院有限公司 | Activated negative electrode with lithium dendrite inhibition effect |
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