CN113363427A - Preparation method of lithium alloy cathode for sulfide all-solid-state battery and battery thereof - Google Patents

Preparation method of lithium alloy cathode for sulfide all-solid-state battery and battery thereof Download PDF

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Publication number
CN113363427A
CN113363427A CN202110633295.6A CN202110633295A CN113363427A CN 113363427 A CN113363427 A CN 113363427A CN 202110633295 A CN202110633295 A CN 202110633295A CN 113363427 A CN113363427 A CN 113363427A
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Prior art keywords
lithium
solid
sulfide
metal
negative electrode
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CN202110633295.6A
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Inventor
刘芳洋
李炳勤
吕娜
蒋良兴
贾明
张宗良
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Hunan Enjie Frontier New Material Technology Co ltd
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Central South University
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

Abstract

The invention provides a preparation method of a lithium alloy cathode for a sulfide all-solid-state battery. The method comprises the following steps: the metal lithium surface is uniformly coated with a layer of metal organic compound with metal activity lower than that of lithium, the metal is replaced by utilizing the fact that the activity of lithium is stronger than that of metal in the compound, and the metal forms a uniform coating layer on the lithium surface to form the lithium alloy negative electrode. The lithium alloy negative electrode can be used for assembling an all-solid-state lithium ion battery. The uniform metal layer on the surface of the lithium alloy cathode can effectively isolate the reaction between the sulfide electrolyte and the metal lithium in the all-solid-state lithium ion battery, and can also inhibit the generation of lithium dendrites to a certain extent, thereby greatly improving the cycling stability and the safety of the all-solid-state lithium ion battery.

Description

Preparation method of lithium alloy cathode for sulfide all-solid-state battery and battery thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a lithium alloy cathode for a sulfide all-solid-state battery and a battery thereof.
Background
The lithium ion battery has the advantages of high energy density, high output power, high monomer voltage, small self-discharge, no memory effect and the like, is widely applied to industries such as consumer electronics, electric automobiles and the like, and also has remarkable advantages in the fields of large-scale energy storage and the like. At present, graphite negative electrodes (with the theoretical specific capacity of 372mAh/g) widely adopted in lithium ion batteries cannot meet the social requirement on higher energy density of the lithium ion batteries, so that the development of novel negative electrode materials is urgently needed. The metal lithium negative electrode has the lowest working potential (-3.04V) and higher theoretical specific capacity (3860mAh/g), and is an excellent negative electrode material of the lithium ion battery.
However, in practical application, the lithium metal negative electrode has the problems of large volume change, easy generation of lithium dendrite and the like, and the safety of the battery is seriously influenced. At present, modification research on a metal lithium negative electrode mainly focuses on the aspects of an artificial SEI film, current collector surface coating, 3D current collector construction, solid electrolyte application and the like, but in practical application, the generation of lithium dendrites is still difficult to completely inhibit, and particularly when the mechanical strength of the solid electrolyte is utilized to block the growth of the lithium dendrites, the sulfide solid electrolyte and the metal lithium can generate interface side reaction, so that the battery impedance can be increased while active lithium is consumed, adverse effects on the battery performance are caused, and the application of the metal lithium negative electrode in a lithium ion battery is still heavy and far.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium alloy cathode for a sulfide all-solid-state battery and the battery thereof, aiming at solving the problem of side reaction between a metal lithium cathode and a sulfide solid-state electrolyte by introducing an alloy protective layer on the premise of ensuring the safety of the battery, and effectively inhibiting the growth of lithium dendrite by the lithium alloy cathode so as to improve the cycle performance and the safety performance of the all-solid-state battery.
In order to achieve the purpose, the invention provides a preparation method of a lithium alloy cathode for a sulfide all-solid-state battery, which comprises the following steps: uniformly coating a layer of metal organic compound with metal activity lower than that of lithium on the surface of metal lithium, and completely reacting to obtain the lithium alloy cathode, wherein the metal in the metal organic compound is one or more of magnesium, aluminum, zinc, indium, tin and silver, and the coating process comprises one or more of coating, smearing, wiping, dipping, dripping, spreading, paving, immersing and flattening to form a uniform layer on the surface of another substance.
Preferably, the magnesium organic compound comprises one or more of magnesium ethoxide, magnesium methoxide, magnesium isopropoxide, and ethylmagnesium bromide.
Preferably, the aluminum organic compound comprises one or more of aluminum triethoxide, aluminum isopropoxide, aluminum butoxide, aluminum sec-butoxide, trimethylaluminum.
Preferably, the zinc organic compound comprises one or more of zinc methoxide, zinc acetate, zinc citrate, zinc oxalate.
Preferably, the indium organic compound comprises one or more of indium acetate, indium trifluoromethanesulfonate, and indium tris (2, 4-pentanedionate).
Preferably, the tin organic compound comprises one or more of diethanotin, methyltin, isopropyltin, tin acetate, trimethyltin chloride, and phenyltin trichloride.
Preferably, the silver organic compound comprises one or more of silver acetate, silver lactate, silver acetylacetonate, silver 1-hydroxy-1-oxopropan-2-ol.
In order to achieve the above object, the present invention provides an all-solid-state lithium ion battery comprising a composite positive electrode, a sulfide solid-state electrolyte, and a lithium alloy negative electrode produced by any one of the above methods.
Preferably, the composite positive electrode is a uniform composite product of a lithium ion battery positive electrode material, a sulfide solid electrolyte and conductive carbon.
Preferably, the sulfide solid state electrolyte comprises Li7P3S11、β-Li3PS4、Li10GePS12、Li9.54Si1.74P1.44S11.7Cl0.3、Li6PS5Cl、Li6PS5Br、Li10SiP2S12、Li7P2S8I、Li9.6P3S12One or more of (a).
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the lithium alloy cathode material used in the invention has higher charge-discharge specific capacity which can reach 3-10 times of that of the graphite cathode used in the current lithium ion battery, and in a battery system with the same quality of cathode material, the consumption of the cathode can be greatly reduced, and the energy density of the battery can be improved;
(2) the metal organic compound used in the invention can be reduced by lithium on the surface of the metal lithium to form a compact metal protective layer, so that the side reaction of the electrolyte and the metal lithium can be effectively prevented, and meanwhile, the metal layer has a lithium ion conduction function and can ensure the normal migration of lithium ions in a negative electrode;
(3) in addition, the compact metal layer is compact and flat, the growth of lithium dendrites can be effectively inhibited, and the safety of the battery is improved.
Drawings
FIG. 1 is a schematic diagram of a lithium alloy cathode prepared by a liquid phase method according to the present invention;
FIG. 2 is a schematic diagram of a lithium alloy cathode prepared by a solid phase method according to the present invention;
FIG. 3 is a schematic structural view of a sulfide all-solid-state battery to which the lithium alloy negative electrode according to the present invention is applied;
FIG. 4 is a first-turn charge-discharge curve diagram of a lithium ion battery prepared in example 1 of the present invention;
fig. 5 is a graph of the cycle performance of the lithium ion battery prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
Example 1:
referring to fig. 1, a metal lithium sheet is immersed in a magnesium ethoxide solution, and is rapidly taken out after 5 seconds, and a lithium magnesium alloy cathode is formed after the reaction is completed; the lithium-magnesium alloy and the anode material LiCoO2Electrolyte Li6PS5Cl and the like to form the solid lithium ion battery. Through detection, the battery of the embodiment has the initial specific discharge capacity of 131.8mAh/g under the current density of 0.1C, the initial coulombic efficiency is 83.17%, the specific discharge capacity after 100 circles is 107mAh/g, and the capacity retention rate after 100 circles is 81.4%.
Example 2:
uniformly spin-coating a zinc acetate solution on the surface of a metal lithium sheet, and waiting for complete reaction to form a lithium-zinc alloy cathode; the lithium-zinc alloy and the anode material LiCoO2Electrolyte Li7P3S11And the like to form the solid-state lithium ion battery. Through detection, the battery of the embodiment has initial specific discharge capacity of 129.8mAh/g under the current density of 0.1C, the initial coulombic efficiency is 82.9%, the specific discharge capacity after 40 circles is 116.5mAh/g, and the capacity retention rate after 40 circles is 89.8%.
Example 3:
dropping sufficient trimethylaluminum solution on the surface of the metal lithium sheet, completely flattening the trimethylaluminum by using an aluminum sheet with an area slightly larger than that of the lithium sheet, and waiting for complete reaction to form a lithium-aluminum alloy cathode; the lithium-aluminum alloy and the positive electrode material LiNi are used0.8Co0.1Mn0.1O2Electrolyte Li9.6P3S12And the like to assemble the lithium ion battery. Through detection, the battery of the embodiment has initial specific discharge capacity of 144.2mAh/g under the current density of 0.3C, the specific discharge capacity after 30 circles is 138.5mAh/g, and the capacity retention rate after 30 circles is 96%.
Example 4:
referring to fig. 2, in a closed container, each surface of the metal lithium sheet is uniformly paved with enough tin acetate particles, and cold pressing is performed for 5min under 0.5MPa, so as to obtain the lithium-tin alloy cathode after the reaction is completed. The lithium-tin alloy and a positive electrode material LiFePO are mixed4Electrolyte Li6PS5Br is assembled into the lithium ion battery. The battery of the present example was tested at 0.1CUnder the current density, the material has the initial specific discharge capacity of 150mAh/g, the specific discharge capacity after 100 circles is 140mAh/g, and the capacity retention rate after 100 circles is 93.3%.

Claims (10)

1. A preparation method of a lithium alloy negative electrode for a sulfide all-solid battery is characterized by comprising the following steps of: uniformly coating a layer of metal organic compound with metal activity lower than that of lithium on the surface of metal lithium, and completely reacting to obtain the lithium alloy cathode, wherein the metal in the metal organic compound is one or more of magnesium, aluminum, zinc, indium, tin and silver, and the coating process comprises one or more of coating, smearing, wiping, dipping, dripping, spreading, paving, immersing and flattening to form a uniform layer on the surface of another substance.
2. The method of making a lithium alloy negative electrode for a sulfide all solid state battery of claim 1, wherein the magnesium organic compound comprises one or more of magnesium ethoxide, magnesium methoxide, magnesium isopropoxide, and ethyl magnesium bromide.
3. The method of preparing a lithium alloy negative electrode for a sulfide all solid state battery according to claim 1, wherein the aluminum organic compound includes one or more of aluminum triethoxide, aluminum isopropoxide, aluminum butoxide, aluminum sec-butoxide, and trimethylaluminum.
4. The method of preparing a lithium alloy negative electrode for a sulfide all-solid battery according to claim 1, wherein the zinc organic compound includes one or more of zinc methoxide, zinc acetate, zinc citrate, and zinc oxalate.
5. The method of manufacturing a lithium alloy negative electrode for a sulfide all-solid battery according to claim 1, wherein the indium organic compound includes one or more of indium acetate, indium trifluoromethanesulfonate, and indium tris (2, 4-pentanedionate).
6. The method of preparing a lithium alloy negative electrode for a sulfide all-solid battery according to claim 1, wherein the tin organic compound includes one or more of diethanotin, methyltin, isopropanotin, tin acetate, trimethyltin chloride, and phenyltin trichloride.
7. The method of preparing a lithium alloy negative electrode for a sulfide all-solid battery according to claim 1, wherein the silver organic compound includes one or more of silver acetate, silver lactate, silver acetylacetonate, and silver 1-hydroxy-1-oxopropan-2-ol.
8. An all-solid-state lithium ion battery comprising a composite positive electrode, a sulfide solid-state electrolyte, and a lithium alloy negative electrode produced by the method of any one of claims 1 to 7.
9. The all-solid-state lithium ion battery according to claim 8, wherein the composite positive electrode is a uniform composite product of a lithium ion battery positive electrode material, a sulfide solid electrolyte, and conductive carbon.
10. The sulfide all-solid battery according to claim 8, wherein the sulfide solid electrolyte comprises Li7P3S11、β-Li3PS4、Li10GePS12、Li9.54Si1.74P1.44S11.7Cl0.3、Li6PS5Cl、Li6PS5Br、Li10SiP2S12、Li7P2S8I、Li9.6P3S12One or more of (a).
CN202110633295.6A 2021-06-07 2021-06-07 Preparation method of lithium alloy cathode for sulfide all-solid-state battery and battery thereof Pending CN113363427A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114050253A (en) * 2021-10-21 2022-02-15 中山大学 Preparation method and application of nano lithium alloy
CN114914422A (en) * 2022-05-19 2022-08-16 武汉理工大学 Composite negative electrode suitable for sulfide all-solid-state battery, preparation method and lithium battery

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Publication number Priority date Publication date Assignee Title
CN106784629A (en) * 2017-01-19 2017-05-31 武汉大学 A kind of lithium metal battery cathode interface method of modifying
CN108011079A (en) * 2017-11-07 2018-05-08 电子科技大学 A kind of surface modification method of lithium anode and application
CN110190251A (en) * 2019-05-09 2019-08-30 华南师范大学 Metal lithium sheet and its preparation method and application
CN112331933A (en) * 2020-10-27 2021-02-05 华中科技大学 Long-cycle-life cathode of aqueous zinc secondary battery and preparation and application thereof
CN112803026A (en) * 2021-02-01 2021-05-14 山东大学 Lithium negative electrode for dendrite-free all-solid-state battery and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784629A (en) * 2017-01-19 2017-05-31 武汉大学 A kind of lithium metal battery cathode interface method of modifying
CN108011079A (en) * 2017-11-07 2018-05-08 电子科技大学 A kind of surface modification method of lithium anode and application
CN110190251A (en) * 2019-05-09 2019-08-30 华南师范大学 Metal lithium sheet and its preparation method and application
CN112331933A (en) * 2020-10-27 2021-02-05 华中科技大学 Long-cycle-life cathode of aqueous zinc secondary battery and preparation and application thereof
CN112803026A (en) * 2021-02-01 2021-05-14 山东大学 Lithium negative electrode for dendrite-free all-solid-state battery and preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114050253A (en) * 2021-10-21 2022-02-15 中山大学 Preparation method and application of nano lithium alloy
CN114914422A (en) * 2022-05-19 2022-08-16 武汉理工大学 Composite negative electrode suitable for sulfide all-solid-state battery, preparation method and lithium battery
CN114914422B (en) * 2022-05-19 2024-03-15 武汉理工大学 Composite negative electrode suitable for sulfide all-solid-state battery, preparation method and lithium battery

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