CN113851647A - Solid electrolyte coated cathode for solid battery and preparation method thereof - Google Patents
Solid electrolyte coated cathode for solid battery and preparation method thereof Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 95
- 239000007787 solid Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims description 41
- 238000000576 coating method Methods 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 19
- 239000007773 negative electrode material Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910021385 hard carbon Inorganic materials 0.000 claims description 6
- 229910021384 soft carbon Inorganic materials 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 5
- 239000011135 tin Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- 229910000676 Si alloy Inorganic materials 0.000 claims description 3
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 239000000463 material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000011031 large-scale manufacturing process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
- 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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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
-
- 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 discloses a solid electrolyte coated cathode for a solid battery and a preparation method thereof. The preparation method effectively improves the lithium ion conductivity of the solid electrolyte coated cathode for the solid battery through the solid electrolyte, and the solid electrolyte coated cathode for the solid battery is applied to the solid lithium ion battery, so that high discharge capacity, perfect rate performance and long cycle performance can be shown.
Description
Technical Field
The invention relates to the field of lithium battery manufacturing, in particular to a solid electrolyte coated negative electrode for a solid battery and a preparation method thereof.
Background
The lithium ion battery is used as a novel energy storage device, and is more and more concerned by people because the energy problem is increasingly prominent; the lithium ion battery has the advantages of high energy density, long cycle life, environmental friendliness and the like, and is widely applied to the fields of electronic equipment, electric automobiles and the like; commercial lithium ion batteries now have achieved an energy density of 300Wh/kg as the technology matures, however further improvements in energy density require new technologies to emerge; in addition, the commercial lithium ion battery generally adopts flammable and explosive organic electrolyte, which brings serious potential safety hazard to the battery; therefore, the solid-state battery becomes the next generation lithium ion battery technology due to its high safety characteristics and high energy density; however, the existing negative electrode materials (graphite, silicon carbon, soft carbon, hard carbon, silicon negative electrode) have not been able to meet the requirements of the solid-state battery for the materials, so it is imperative to develop a negative electrode material for the solid-state battery.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a solid electrolyte coated negative electrode for a solid battery and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first aspect of the invention provides a preparation method of a solid electrolyte coated cathode for a solid battery, which comprises the steps of coating a solid electrolyte on the surface of a cathode material by a solution method, and carrying out heat treatment to obtain the solid electrolyte coated cathode for the solid battery.
Preferably, the method comprises the following steps:
s1, preparing a solid coating by a solution method, dispersing a solid electrolyte and a negative electrode material in an aqueous solution or an organic solvent-aqueous solution, and stirring to obtain the solid coating;
s2, the solid coating is heat-treated to obtain a solid electrolyte-coated negative electrode for a solid battery.
Preferably, in the step S1, the solid electrolyte is selected from Li3InCl6、Li3InBr6、Li3YCl6、Li3YBr6、Li3ScCl6、Li3ErCl6、Li3TbCl6、Li3YbCl6、Li3LuCl6、Li2.1Zr0.9Sc0.1Cl6、Li2.15Zr0.85Sm0.15Cl6、Li2.07Zr0.82I0.21Cl6One or more of (a).
Preferably, in step S1, the negative electrode material is selected from one of graphite, silicon carbon, soft carbon, hard carbon, silicon, tin, silicon oxide, tin oxide, silicon alloy, and tin alloy.
Preferably, in step S1, the organic solvent in the organic solvent-water solution is selected from one or more of ethanol, tetrahydrofuran, methanol, isopropanol, chloroform, tetrachloromethane, toluene, acetone, methyl acetate, ethyl acetate, and propyl acetate.
Preferably, in step S1, the mass ratio of the solid electrolyte to the anode material is 1: 10-1: 1000.
preferably, in the step S1, the stirring temperature is 40 to 150 ℃, the stirring speed is 100 to 2000 rpm, and the stirring time is 0.5 to 24 hours.
Preferably, in step S2, the atmosphere of the heat treatment is selected from one or more of nitrogen, argon, helium and hydrogen.
Preferably, in step S2, the heat treatment atmosphere is a vacuum atmosphere.
Preferably, in the step S2, the heat treatment temperature is 100 to 250 ℃, and the heat treatment time is 1 to 48 hours.
A second aspect of the invention provides a solid-state electrolyte-coated negative electrode for a solid-state battery, which is produced according to the production method of the first aspect.
The invention has the beneficial effects that:
1. according to the preparation method of the solid electrolyte coated negative electrode for the solid battery, the solid electrolyte coated negative electrode for the solid battery is synthesized by adopting a solution method and heat treatment, and the lithium ion conductivity of the solid electrolyte coated negative electrode for the solid battery is effectively improved through the solid electrolyte, so that the impedance and the polarization degree are effectively reduced, and the purpose of improving the electrochemical performance of the lithium battery is realized;
2. the solid-state battery of the invention uses the solid-state electrolyte to coat the negative pole, its lithium ion conductivity can be controlled by the solid-state electrolyte added;
3. according to the preparation method of the solid electrolyte coated cathode for the solid battery, disclosed by the invention, the content of the solid electrolyte is accurately controlled, so that large-scale production is realized;
4. the preparation method of the solid electrolyte coated cathode for the solid battery has the advantages of low cost, simple and convenient process and easy large-scale production.
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 an XRD spectrum of a solid electrolyte-coated graphite negative electrode for a solid-state battery prepared in example 1;
FIG. 2 shows a solid electrolyte coated negative electrode of 200mAg for the solid-state battery prepared in example 1-1Charge and discharge cycle curves at current density.
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.
The invention provides a preparation method of a solid electrolyte coated cathode for a solid battery, which comprises the steps of coating a solid electrolyte on the surface of a cathode material by a solution method, and carrying out heat treatment to obtain the solid electrolyte coated cathode for the solid battery; the method specifically comprises the following steps:
s1, preparing a solid electrolyte coating by a solution method, dispersing a solid electrolyte and a negative electrode material in an aqueous solution or an organic solvent-aqueous solution, and stirring to volatilize a solvent to obtain the solid electrolyte coating;
wherein the solid electrolyte is selected from Li3InCl6、Li3InBr6、Li3YCl6、Li3YBr6、Li3ScCl6、Li3ErCl6、Li3TbCl6、Li3YbCl6、Li3LuCl6、Li2.1Zr0.9Sc0.1Cl6、Li2.15Zr0.85Sm0.15Cl6、Li2.07Zr0.82I0.21Cl6One or more of; the negative electrode material is selected from one of graphite, silicon carbon, soft carbon, hard carbon, silicon, tin, silicon monoxide, tin oxide, silicon alloy and tin alloy; the organic solvent in the aqueous solution is selected from one or more of ethanol, tetrahydrofuran, methanol, isopropanol, chloroform, tetrachloromethane, toluene, acetone, methyl acetate, ethyl acetate and propyl acetate; the mass ratio of the solid electrolyte to the anode material is 1: 10-1: 1000, parts by weight; and during stirring, the stirring temperature is 40-150 ℃, the stirring speed is 100-2000 rpm, and the stirring time is 0.5-24 h.
S2, the solid electrolyte coating is heat-treated to obtain a solid electrolyte-coated negative electrode for a solid battery.
Wherein the heat treatment atmosphere is selected from one or more of nitrogen, argon, helium and hydrogen, or the heat treatment atmosphere adopts a vacuum atmosphere; the heat treatment temperature is 100-350 ℃, and the heat treatment time is 1-48 h.
The solid electrolyte-coated negative electrode for a solid-state battery and the method for producing the same according to the present invention will be further described with reference to specific examples;
example 1
S1, preparing a solid electrolyte coating by a solution method, dispersing the solid electrolyte and a negative electrode material in an aqueous solution or an organic solvent-aqueous solution, and stirring to obtain the solid coating;
mixing Li3InCl6Dispersing graphite and graphite in an aqueous solution according to the ratio of 2:100, stirring at 100 ℃ for 12h to volatilize water, and stirring at the speed of 300 r/min to obtain a powdery solid electrolyte coating;
s2, the solid electrolyte coating is heat-treated to obtain a solid electrolyte-coated negative electrode for a solid battery.
And (3) putting the powdery solid electrolyte coating material into a tube furnace for heat treatment, and treating for 12h under the vacuum atmosphere condition of 250 ℃ to obtain the solid electrolyte coated graphite cathode for the solid battery.
Example 2
S1, preparing a solid electrolyte coating by a solution method, dispersing the solid electrolyte and a negative electrode material in an aqueous solution or an organic solvent-aqueous solution, and stirring to obtain the solid coating;
mixing Li3InCl6Dispersing silicon and carbon in an aqueous solution according to the proportion of 3:100, stirring for 8 hours at 100 ℃ to volatilize water, and stirring at the speed of 500 r/min to obtain a powdery solid electrolyte coating;
s2, the solid electrolyte coating is heat-treated to obtain a solid electrolyte-coated negative electrode for a solid battery.
And (3) putting the powdery solid electrolyte coating into a tube furnace for heat treatment, and treating for 24h under the condition of a vacuum atmosphere at 280 ℃ to obtain the solid electrolyte coated silicon-carbon cathode for the solid battery.
Example 3
S1, preparing a solid electrolyte coating by a solution method, dispersing the solid electrolyte and a negative electrode material in an aqueous solution or an organic solvent-aqueous solution, and stirring to obtain the solid coating;
mixing Li3YCl6Dispersing soft carbon in water solution at a ratio of 5:100, stirring at 150 deg.C for 12 hr to volatilize water, stirring at 200 rpm to obtain powdered solid electrolyte coatingAn agent;
s2, the solid electrolyte coating is heat-treated to obtain a solid electrolyte-coated negative electrode for a solid battery.
And (3) putting the powdery solid electrolyte coating material into a tube furnace for heat treatment, and treating for 12h under the vacuum atmosphere condition of 350 ℃ to obtain the solid electrolyte coated soft carbon negative electrode for the solid battery.
Example 4
S1, preparing a solid electrolyte coating by a solution method, dispersing a solid electrolyte and a negative electrode material in an aqueous solution or an organic solvent-aqueous solution, and stirring to obtain the solid electrolyte coating;
mixing Li3YCl6Dispersing the hard carbon and the acetone-water solution according to the proportion of 10:100, stirring for 12 hours at the temperature of 120 ℃ to volatilize the solvent, and stirring at the speed of 250 revolutions per minute to obtain a powdery solid coating;
s2, the solid electrolyte coating is heat-treated to obtain a solid electrolyte-coated negative electrode for a solid battery.
And (3) putting the powdery solid electrolyte coating material into a tube furnace for heat treatment, and treating for 6h under the vacuum atmosphere condition of 150 ℃ to obtain the solid electrolyte coated hard carbon negative electrode for the solid battery.
Example 5
S1, preparing a solid electrolyte coating by a solution method, dispersing a solid electrolyte and a negative electrode material in an aqueous solution or an organic solvent-aqueous solution, and stirring to obtain the solid electrolyte coating;
mixing Li3YCl6Dispersing silicon and the silicon in a methanol-water solution according to the ratio of 4:100, stirring for 6 hours at 120 ℃ to volatilize the solvent, wherein the stirring speed is 350 r/m, and obtaining a powdery solid electrolyte coating material;
s2, the solid electrolyte coating is heat-treated to obtain a solid electrolyte-coated negative electrode for a solid battery.
And (3) putting the powdery solid electrolyte coating into a tube furnace for heat treatment, and treating for 15h under the vacuum atmosphere condition of 120 ℃ to obtain the solid electrolyte coated silicon negative electrode for the solid battery.
Example 6
S1, preparing a solid electrolyte coating by a solution method, dispersing the solid electrolyte and a negative electrode material in an aqueous solution or an organic solvent-aqueous solution, and stirring to obtain the solid coating;
mixing Li3YCl6And tin are dispersed in the ethanol-water solution according to the ratio of 4:100, the solvent is volatilized after stirring for 6 hours at the temperature of 125 ℃, and the stirring speed is 450 revolutions per minute, so that powdery solid coating materials are obtained;
s2, the solid electrolyte coating is heat-treated to obtain a solid electrolyte-coated negative electrode for a solid battery.
And (3) putting the powdery solid electrolyte coating into a tube furnace for heat treatment, and treating for 18h under the condition of a vacuum atmosphere at 160 ℃ to obtain the solid electrolyte coated tin negative electrode for the solid battery.
As shown in fig. 1, the XRD diffraction peak shown in the XRD spectrum of the solid electrolyte-coated graphite negative electrode for solid-state batteries prepared in example 1 was mainly graphite, indicating that the crystal structure of graphite was not changed by the solid electrolyte coating; as shown in fig. 2, the solid electrolyte-coated graphite negative electrode for solid-state battery prepared in example 1 was used as a negative electrode at 200mAg-1Charging and discharging at current density, and after 120 times of circulation, the capacity is still maintained at 394mAhg-1The coulombic efficiency remained at 100%.
With reference to embodiments 1 to 6, the method for preparing the solid electrolyte coated negative electrode for the solid battery, disclosed by the invention, adopts a solution method and a heat treatment to synthesize the solid electrolyte coated negative electrode for the solid battery, and the solid electrolyte with high lithium ion conductivity is added, so that the effect of a contact surface between an active material and the solid electrolyte can be increased, and a transmission network of electrons and lithium ions is formed, thereby being beneficial to reducing the interface impedance and polarization among the active materials in an electrode plate and achieving the purpose of improving the electrochemical performance of a lithium battery; the solid-state battery is provided with a negative electrode coated with a solid-state electrolyte, and the lithium ion conductivity of the negative electrode can be controlled by the added solid-state electrolyte; the preparation method of the solid electrolyte coated cathode for the solid-state battery realizes large-scale production by accurately controlling the content of the solid electrolyte; the preparation method of the solid electrolyte coated cathode for the solid battery has the advantages of low cost, simple and convenient process and easy large-scale production.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. A preparation method of a solid electrolyte coated cathode for a solid battery is characterized in that a solution method is adopted to coat a solid electrolyte on the surface of a cathode material, and then the solid electrolyte coated cathode for the solid battery is obtained through heat treatment.
2. The method of claim 1, comprising the steps of:
s1, preparing a solid coating by a solution method, dispersing a solid electrolyte and a negative electrode material in an aqueous solution or an organic solvent-aqueous solution, and stirring to obtain the solid coating;
s2, the solid coating is heat-treated to obtain a solid electrolyte-coated negative electrode for a solid battery.
3. The method according to claim 2, wherein in step S1, the solid electrolyte is selected from Li3InCl6、Li3InBr6、Li3YCl6、Li3YBr6、Li3ScCl6、Li3ErCl6、Li3TbCl6、Li3YbCl6、Li3LuCl6、Li2.1Zr0.9Sc0.1Cl6、Li2.15Zr0.85Sm0.15Cl6、Li2.07Zr0.82I0.21Cl6One or more of (a).
4. The method according to claim 2, wherein in step S1, the negative electrode material is selected from one of graphite, silicon carbon, soft carbon, hard carbon, silicon, tin, silicon oxide, tin oxide, silicon alloy, and tin alloy.
5. The method according to claim 2, wherein in step S1, the organic solvent in the organic solvent-aqueous solution is selected from one or more of ethanol, tetrahydrofuran, methanol, isopropanol, chloroform, tetrachloromethane, toluene, acetone, methyl acetate, ethyl acetate, and propyl acetate.
6. The production method according to claim 2, wherein in the step S1, the mass ratio of the solid electrolyte to the anode material is 1: 10-1: 1000.
7. the method according to claim 2, wherein in the step S1, the stirring temperature is 40-150 ℃, the stirring speed is 100-2000 rpm, and the stirring time is 0.5-24 hours.
8. The method according to claim 2, wherein in step S2, the atmosphere of the heat treatment is selected from one or more of nitrogen, argon, helium, and hydrogen.
9. The method according to claim 2, wherein in step S2, an atmosphere of the heat treatment is a vacuum atmosphere.
10. The method according to claim 2, wherein in step S2, the heat treatment temperature is 100-350 ℃ and the heat treatment time is 1-48 h.
11. A solid electrolyte coated negative electrode for a solid-state battery, characterized by being prepared by the preparation method according to any one of claims 1 to 10.
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| CN202010596661.0A CN113851647A (en) | 2020-06-28 | 2020-06-28 | Solid electrolyte coated cathode for solid battery and preparation method thereof |
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| CN116314834A (en) * | 2023-05-25 | 2023-06-23 | 四川新能源汽车创新中心有限公司 | Composite anode material, preparation method thereof and all-solid-state battery |
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Effective date of registration: 20230109 Address after: Weisan Road Chemical Office Building, Baoshan District, Shanghai, 2004 Applicant after: Baowu Carbon Technology Co.,Ltd. Applicant after: BAOSHAN IRON & STEEL Co.,Ltd. Address before: 201900 Fujin Road, Baoshan District, Shanghai 885 Applicant before: BAOSHAN IRON & STEEL Co.,Ltd. |
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Application publication date: 20211228 |