CN109428138B - Preparation method of lithium-air battery and lithium-air battery - Google Patents
Preparation method of lithium-air battery and lithium-air battery Download PDFInfo
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- CN109428138B CN109428138B CN201710736352.7A CN201710736352A CN109428138B CN 109428138 B CN109428138 B CN 109428138B CN 201710736352 A CN201710736352 A CN 201710736352A CN 109428138 B CN109428138 B CN 109428138B
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- air battery
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 59
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006258 conductive agent Substances 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 229910000676 Si alloy Inorganic materials 0.000 claims abstract description 10
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007773 negative electrode material Substances 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 8
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 238000004806 packaging method and process 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
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 230000002687 intercalation Effects 0.000 claims description 3
- 238000009830 intercalation Methods 0.000 claims description 3
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 229910013553 LiNO 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
- 229910052737 gold Inorganic materials 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-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
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 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
- 229910052697 platinum 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
- 239000011863 silicon-based powder Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 26
- 239000002184 metal Substances 0.000 abstract description 26
- 239000002210 silicon-based material Substances 0.000 abstract description 8
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- 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
- 239000002002 slurry Substances 0.000 description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 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
- 239000010406 cathode material Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-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
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000446 fuel Substances 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
- 230000002427 irreversible effect Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 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
- 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
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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
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- 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 invention provides a preparation method of a lithium-air battery without metal lithium, which comprises the following steps: (1) mixing and coating a silicon-based negative electrode material, a conductive agent and a binder on a negative electrode current collector; (2) mixing and pressing a catalyst, a conductive agent, a binder and lithium nitride to a positive current collector in an anhydrous and oxygen-free environment; (3) and (3) separating the positive electrode and the negative electrode by using a diaphragm in an anhydrous and oxygen-free environment, and dropwise adding an electrolyte to assemble the lithium-air battery. According to the lithium-silicon alloy cathode, lithium nitride is used as a lithium source, a silicon-based material is used as a cathode, the lithium-silicon alloy cathode is formed during the first charging, metal lithium is replaced, lithium dendrite is avoided, and a discharge product lithium peroxide can be effectively stored in a vacancy generated by decomposition of the lithium nitride.
Description
Technical Field
The invention relates to a preparation method of a lithium-air battery, belonging to the technical field of fuel cells.
Background
With the increasing urgency of energy demand in modern society, high energy density secondary batteries have become the key point of future energy industry development, and lithium ion batteries have become the most popular secondary batteries with their outstanding performance advantages. However, the cathode material commonly used in the existing lithium ion battery is graphitized carbon, the theoretical specific capacity of the graphitized carbon is 370mAh/g, the anode material is lithium iron phosphate, lithium cobaltate, lithium manganate or ternary material, and the actual specific capacity of the graphitized carbon far cannot meet the requirements of the modern society. Particularly, the rapid development of electric automobiles puts higher demands on the development of high-specific energy lithium ion batteries. The high specific energy advantage of the lithium metal-based battery system is becoming more and more a hot point and a development direction of research, such as lithium-sulfur battery and lithium-air battery, the theoretical energy density of the Li/S battery can be as high as 2600Wh/Kg, and the energy density of the lithium-air battery can be as high as 3500Wh/Kg, which is far higher than the energy density of about 200Wh/Kg of the current conventional lithium ion battery. However, the adoption of the metal lithium as the cathode material of the secondary battery has two main problems, namely, the metal lithium has high activity, so that the metal lithium is easy to have irreversible reaction with the electrolyte in the circulating process, the electrolyte is consumed, the coulomb efficiency is reduced, and the final failure is caused; and dendritic crystals formed by metal lithium and 'dead lithium' in the circulating process can also reduce the circulating efficiency of the lithium electrode, and if the lithium dendritic crystals continuously grow, the lithium dendritic crystals can pierce a diaphragm to cause short circuit and even explosion and other safety problems. In particular, since the lithium-air battery is a semi-open system, protection of metallic lithium is a troublesome problem. Therefore, the search for a high specific capacity negative electrode material which can replace the metal lithium is of great significance.
The silicon material has a theoretical specific capacity as high as 4200mAh/g and a lower charge-discharge platform compared with lithium, but if the silicon material is used for a lithium-air battery, the silicon material must firstly react with lithium to form an alloy, the lithium-silicon alloy has active chemical properties, the preparation of an electrode is difficult, and the performance is unstable. Therefore, the silicon-based negative electrode material has great challenges in application to lithium air batteries.
Disclosure of Invention
The invention aims to provide a method for manufacturing a lithium-air battery without metal lithium and the lithium-air battery manufactured by the method, wherein a silicon-based material is adopted as a negative electrode, so that the problems of low coulomb efficiency, low safety and lithium dendrite existing in the metal lithium are solved. The lithium-air battery uses lithium nitride as a lithium source, in-situ electrochemical lithium intercalation of a silicon-based negative electrode is realized by assembling the lithium-air battery at one time, and a vacancy generated by decomposition of the lithium nitride can effectively store a discharge product of the lithium-air battery. The preparation method of the lithium-air battery without the metal lithium is simple to operate and easy to realize industrial application.
The invention is realized by the following technical scheme:
in a first aspect, the present invention provides a method for preparing a lithium-air battery, comprising the steps of:
respectively preparing a battery cathode and a battery anode;
sequentially packaging the battery anode, the diaphragm and the battery cathode in an anhydrous and oxygen-free environment, and dropwise adding an electrolyte to obtain the lithium-air battery;
the preparation method of the battery cathode comprises the following steps:
and uniformly mixing the silicon-based negative electrode material, the conductive agent and the adhesive, coating the mixture on a negative current collector, and drying to obtain the battery negative electrode.
Preferably, the conductive agent for the negative electrode is one or more of acetylene black, Super P, Ketjen black and conductive graphite.
Preferably, the binder for the negative electrode is one or more of polyacrylic acid, sodium alginate, sodium carboxymethylcellulose, polyvinylidene fluoride, cyclodextrin, arabic gum, xanthan gum and guar gum.
Preferably, the preparation method of the battery positive electrode comprises the following steps:
and in an anhydrous and oxygen-free environment, uniformly mixing the lithium nitride, the catalyst, the conductive agent and the adhesive, and pressing the mixture on a positive current collector to obtain the battery positive electrode.
Preferably, the material of the positive electrode current collector is foamed nickel or carbon paper.
Preferably, the content of the catalyst in the battery positive electrode is 1-10%.
Preferably, the catalyst is carbon nanotube, Pt, Ru, Pd, Ag, Au, RuO2、MnO2、Co3O4、Fe3O4One or more of them.
Preferably, the conductive agent for the positive electrode is one or more of acetylene black, Super P, Ketjen black and conductive graphite.
Preferably, the binder is PTFE.
Preferably, the negative electrode current collector is a copper foil.
Preferably, the silicon-based negative electrode material is one or more selected from nano silicon powder, micron silicon powder, a silicon/carbon composite material, silica and a silica/carbon composite material.
Preferably, the electrolyte comprises a lithium salt selected from the group consisting of LiNO and a solvent3、LiPF6、LiTFSI、LiFSI、LiClO4、LiCF3SO3The solvent is one or more selected from ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethyl sulfoxide and N, N-dimethylformamide.
Preferably, the electrolyte further comprises a film forming additive, the mass fraction of the film forming additive in the electrolyte is 1-5%, and the film forming additive is preferably fluoroethylene carbonate.
Preferably, the capacity ratio of the positive electrode material to the negative electrode material is 1.05-1.2.
In the invention, nitrogen and lithium ions are generated after the lithium nitride is decomposed;
the nitrogen is released through the air electrode, and lithium ions reach the negative electrode through the electrolyte and react with silicon to form the lithium-silicon alloy.
In a second aspect, the present invention also provides a lithium air battery prepared by the foregoing method.
The lithium nitride has a theoretical specific capacity of 2300mAh/g, can be decomposed at a lower potential (about 1V relative to metallic lithium), and the decomposition products are lithium ions and nitrogen gas, and the generated nitrogen gas is easily removed because the lithium-air battery is a semi-open system.
Compared with the prior art, the invention has the following beneficial effects:
1. the silicon-based material is used for replacing metal lithium as a negative electrode material of the lithium air battery, the efficiency of the metal lithium in the lithium air battery is 20% -30%, the silicon-based material has the efficiency of more than 90%, and the problems of low efficiency, low safety and dendritic crystal caused by the metal lithium are avoided;
2. the lithium nitride is used as a lithium source, and the battery is manufactured at one time to form a lithium-silicon alloy cathode, so that the lithium air battery with excellent performance is obtained.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a first-turn charge curve of a lithium-air battery without metallic lithium prepared in example 1 of the present invention;
FIG. 2 is the charge and discharge curves of circles 2 and 5 of a lithium-air battery without metallic lithium prepared in example 1 of the present invention;
FIG. 3 is a first turn charge curve of a lithium-air battery made in example 3 of the present invention without lithium metal;
FIG. 4 shows the charge and discharge curves of circles 2, 5 and 10 of the lithium-air battery without metallic lithium prepared in example 3 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The method for manufacturing the lithium-air battery without the metal lithium comprises the following steps of:
(1) mixing nano silicon powder, a conductive agent and a binder to prepare slurry, coating the slurry on a copper foil, and drying in vacuum to obtain a battery negative electrode part;
(2) fully mixing the lithium nitride, the carbon nano tube, the conductive agent and the binder in an anhydrous and oxygen-free environment, and pressing the mixture on the foamed nickel to form a positive electrode part;
(3) and packaging the prepared positive electrode, the diaphragm and the negative electrode in an anhydrous and oxygen-free environment, and dropwise adding an electrolyte.
Thus, the lithium-air battery without the metal lithium is manufactured.
The lithium-air battery without metallic lithium prepared in this example has a charge-discharge curve as shown in fig. 1, the decomposition of lithium nitride is mainly around 1V, after charging to 3.5V, the lithium nitride is almost completely decomposed, and a lithium-silicon alloy is formed at the negative electrode, the lithium-air battery without metallic lithium prepared in example 1 of this invention has a charge-discharge curve as shown in fig. 2 at circles 2 and 5, the lithium-silicon alloy is used as the negative electrode, the carbon nanotube is used as the catalyst, and the capacity of 0.9mAh cm in oxygen-2The normal cycle can be realized by charging and discharging, and the charging overpotential is small.
Example 2
The method for manufacturing the lithium-air battery without the metal lithium comprises the following steps of:
(1) mixing nano silicon powder, a conductive agent and a binder to prepare slurry, coating the slurry on a copper foil, and drying in vacuum to obtain a battery negative electrode part;
(2) in an anhydrous and oxygen-free environment, fully mixing lithium nitride, a carbon-supported Ru catalyst, a conductive agent and a binder, and pressing the mixture on foamed nickel to form a positive electrode part;
(3) and packaging the prepared positive electrode, the diaphragm and the negative electrode in an anhydrous and oxygen-free environment, and dropwise adding an electrolyte.
Thus, the lithium-air battery without the metal lithium is manufactured.
Example 3
The method for manufacturing the lithium-air battery without the metal lithium comprises the following steps of:
(1) mixing silicon monoxide, a conductive agent and a binder to prepare slurry, coating the slurry on a copper foil, and drying in vacuum to obtain a battery negative electrode part;
(2) fully mixing the lithium nitride, the carbon nano tube, the conductive agent and the binder in an anhydrous and oxygen-free environment, and pressing the mixture on the foamed nickel to form a positive electrode part;
(3) and packaging the prepared positive electrode, the diaphragm and the negative electrode in an anhydrous and oxygen-free environment, and dropwise adding an electrolyte.
Thus, the lithium-air battery without the metal lithium is manufactured.
The lithium-air battery without metallic lithium prepared in this example has a charge-discharge curve as shown in fig. 3, the decomposition of lithium nitride is mainly around 1V, after charging to 3.5V, lithium nitride is almost completely decomposed, lithium ions and silicon monoxide form a lithium-silicon alloy at the negative electrode, the lithium-air battery without metallic lithium prepared in example 3 of the present invention has a charge-discharge curve as shown in fig. 4 at circles 2, 5 and 10, the lithium-silicon alloy serves as the negative electrode, carbon nanotubes serve as the catalyst, and the capacity of 0.18mAh cm in oxygen-2Charging and discharging can be performed to realize normal circulation, and the battery is chargedThe potential is small.
Example 4
The method for manufacturing the lithium-air battery without the metal lithium comprises the following steps of:
(1) mixing silicon monoxide, a conductive agent and a binder to prepare slurry, coating the slurry on a copper foil, and drying in vacuum to obtain a battery negative electrode part;
(2) in an anhydrous and oxygen-free environment, fully mixing lithium nitride, a carbon-supported Ru catalyst, a conductive agent and a binder, and pressing the mixture on foamed nickel to form a positive electrode part;
(3) and packaging the prepared positive electrode, the diaphragm and the negative electrode in an anhydrous and oxygen-free environment, and dropwise adding an electrolyte.
Thus, the lithium-air battery without the metal lithium is manufactured.
Example 5
Adopts a silicon protoxide material as a negative electrode and RuO carried by carbon2The catalyst is a positive electrode catalyst, and the manufacturing method of the lithium-air battery without metal lithium comprises the following steps:
(1) mixing silicon monoxide, a conductive agent and a binder to prepare slurry, coating the slurry on a copper foil, and drying in vacuum to obtain a battery negative electrode part;
(2) in an anhydrous and oxygen-free environment, the lithium nitride and the carbon are loaded with RuO2Fully mixing the catalyst, the conductive agent and the binder, and pressing the mixture on the foamed nickel to form a positive electrode part;
(3) and packaging the prepared positive electrode, the diaphragm and the negative electrode in an anhydrous and oxygen-free environment, and dropwise adding an electrolyte.
Thus, the lithium-air battery without the metal lithium is manufactured.
In summary, the invention provides a method for manufacturing a lithium-air battery without metal lithium and a lithium-air battery manufactured by the method, wherein a silicon-based material is used as a negative electrode, so that the problems of low coulomb efficiency, low safety and lithium dendrite existing in metal lithium are solved. The lithium-air battery uses lithium nitride as a lithium source, in-situ electrochemical lithium intercalation of a silicon-based negative electrode is realized by assembling the lithium-air battery at one time, and a vacancy generated by decomposition of the lithium nitride can effectively store a discharge product of the lithium-air battery. The preparation method of the lithium-air battery without the metal lithium is simple to operate and easy to realize industrial application.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (8)
1. A preparation method of a lithium-air battery is characterized by comprising the following steps:
respectively preparing a battery cathode and a battery anode;
sequentially packaging the battery anode, the diaphragm and the battery cathode in an anhydrous and oxygen-free environment, and dropwise adding an electrolyte to obtain the lithium-air battery;
the preparation method of the battery cathode comprises the following steps:
uniformly mixing a silicon-based negative electrode material, a conductive agent and an adhesive, coating the mixture on a negative current collector, and drying to obtain the battery negative electrode;
the preparation method of the battery anode comprises the following steps:
uniformly mixing lithium nitride, a catalyst, a conductive agent and an adhesive in an anhydrous and oxygen-free environment, and pressing the mixture on a positive current collector to obtain a battery positive electrode;
generating nitrogen and lithium ions after the lithium nitride is decomposed, releasing the nitrogen through an air electrode, and enabling the lithium ions to reach a negative electrode through electrolyte to react with silicon to form a lithium-silicon alloy;
the lithium-air battery uses lithium nitride as a lithium source, in-situ electrochemical lithium intercalation of a silicon-based negative electrode is realized by assembling the lithium-air battery at one time, and a vacancy generated by decomposition of the lithium nitride is used for storing a discharge product of the lithium-air battery.
2. The method of manufacturing a lithium-air battery according to claim 1, wherein the material of the positive electrode current collector is foamed nickel or carbon paper.
3. The method of claim 1, wherein the catalyst is carbon nanotubes, Pt, Ru, Pd, Ag, Au, RuO2、MnO2、Co3O4、Fe3O4One or more of them.
4. The method of claim 1, wherein the binder is PTFE.
5. The method of manufacturing a lithium-air battery of claim 1, wherein the negative current collector is a copper foil.
6. The method according to claim 1, wherein the silicon-based negative electrode material is selected from one or more of nano silicon powder, micro silicon powder, a silicon/carbon composite material, silica and a silica/carbon composite material.
7. The method of claim 1, wherein the electrolyte comprises a lithium salt selected from the group consisting of LiNO and a solvent3、LiPF6、LiTFSI、LiFSI、LiClO4、LiCF3SO3The solvent is one or more selected from ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethyl sulfoxide and N, N-dimethylformamide.
8. A lithium air battery prepared by the method of claim 1.
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| CN109860958B (en) * | 2019-02-02 | 2020-09-11 | 北京师范大学 | Lithium-carbon dioxide battery and preparation method thereof |
| CN112786313A (en) * | 2019-11-04 | 2021-05-11 | 中国科学院大连化学物理研究所 | Electrode slurry containing lithium nitride and preparation and application thereof |
| KR102477409B1 (en) * | 2020-12-21 | 2022-12-15 | 동국대학교 산학협력단 | Air electrode for Lithium Air Battery and Method of manufacturing the same |
| CN114824587A (en) * | 2022-05-30 | 2022-07-29 | 中国科学院长春应用化学研究所 | Lithium air/carbon fluoride composite battery |
| CN114899348B (en) * | 2022-06-21 | 2023-06-23 | 天目湖先进储能技术研究院有限公司 | Active negative electrode with lithium dendrite inhibition effect |
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