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CN115172669B - A battery silicon negative electrode, preparation method, sulfide all-solid-state lithium battery and application - Google Patents

A battery silicon negative electrode, preparation method, sulfide all-solid-state lithium battery and application Download PDF

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CN115172669B
CN115172669B CN202210793959.XA CN202210793959A CN115172669B CN 115172669 B CN115172669 B CN 115172669B CN 202210793959 A CN202210793959 A CN 202210793959A CN 115172669 B CN115172669 B CN 115172669B
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battery
silicon
negative electrode
lithium
temperature control
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CN115172669A (en
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孙振
轩敏杰
罗明
姜珖中
肖维东
吕娜
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High Energy Era Zhuhai New Energy Technology Co ltd
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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
    • H01M4/134—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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • 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
    • 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
    • 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
    • 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

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  • Electrochemistry (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

本公开提供一种电池硅负极、制备方法、硫化物全固态锂电池以及应用，所述制备方法包括如下步骤：将锂化物置于恒温反应容器第一控温区，硼化物置于恒温反应容器第二控温区，硅球或硅棒置于恒温反应容器内第三控温区；向恒温反应容器通入惰性气体，使得锂化物和硼化物气相包覆在硅球或硅棒表面；将惰性气体切换为氧气通入恒温反应容器，设置第三控温区温度为200‑400℃，使得纳米硅球或硅棒表面的锂化物和硼化物氧化成Li‑B‑O包覆层；将氧气切换为二氧化碳气体通入恒温反应容器，设置第三控温区温度为400‑800℃，使得Li‑B‑O包覆层转变为Li‑B‑C‑O包覆层，本公开能够提升Si负极在硫化物全固态电池的倍率性能和长循环稳定性。

The present invention provides a battery silicon negative electrode, a preparation method, a sulfide all-solid-state lithium battery and an application. The preparation method comprises the following steps: placing a lithium compound in a first temperature control zone of a constant temperature reaction container, placing a boride in a second temperature control zone of the constant temperature reaction container, and placing a silicon ball or a silicon rod in a third temperature control zone of the constant temperature reaction container; introducing an inert gas into the constant temperature reaction container so that the lithium compound and the boride are gaseously coated on the surface of the silicon ball or the silicon rod; switching the inert gas to oxygen gas and introducing it into the constant temperature reaction container, setting the temperature of the third temperature control zone to 200-400°C, so that the lithium compound and the boride on the surface of the nano silicon ball or the silicon rod are oxidized into a Li-B-O coating layer; switching the oxygen to carbon dioxide gas and introducing it into the constant temperature reaction container, setting the temperature of the third temperature control zone to 400-800°C, so that the Li-B-O coating layer is converted into a Li-B-C-O coating layer. The present invention can improve the rate performance and long cycle stability of the Si negative electrode in the sulfide all-solid-state battery.

Description

Battery silicon negative electrode, preparation method, sulfide all-solid-state lithium battery and application
Technical Field
The disclosure relates to the field of batteries, and in particular relates to a silicon negative electrode of a battery, a preparation method, a lithium battery and application.
Background
Sulfide solid state electrolytes have received considerable attention at present due to their high ionic conductivity. The composition of an all-solid-state battery with high energy density by combining a sulfide solid-state electrolyte with a high-capacity metallic lithium negative electrode (3870 mAh g-1) has become a main stream development direction in the future. However, the use of metallic lithium negative electrodes has the problems of instability with sulfide solid state electrolytes, easy battery short circuit and the like at present.
In order to solve the above-mentioned problems, the related art has been mainly to avoid the use of metallic lithium negative electrodes, and instead, some high-voltage negative electrode materials, such as metallic In and lithium titanate negative electrodes, etc., or some low-voltage low-capacity negative electrodes, such as graphite, etc., are used. However, the adoption of In or lithium titanate negative electrodes has the problem of high voltage platform, which can lead to further reduction of the specific capacity of the whole battery and limit the overall energy density of the battery, and the graphite negative electrode can also cause similar negative effects.
In addition to the above operations, there are also related art that employ a high specific capacity Si negative electrode to increase the energy density of the negative electrode side in the cell, thereby increasing the energy density of the overall battery. However, si negative electrodes have a plurality of problems in sulfide all-solid batteries, namely, on one hand, the lithium ion conductivity of pure Si is low, so that the multiplying power performance of the Si negative electrode is poor, and on the other hand, the electronegativity of S in Si and sulfide solid electrolytes is different, so that a Li+ space charge layer is easily formed at the electrolyte and Si interface layer, the rapid transmission of lithium ions is resisted, and the multiplying power performance of the silicon negative electrode is further influenced.
Disclosure of Invention
The disclosure provides a silicon anode of a battery, a preparation method, a lithium battery and application, which can solve one or more technical problems mentioned in the background art. In order to solve the technical problems, the present disclosure provides the following technical solutions:
As one aspect of the embodiments of the present disclosure, a battery silicon negative electrode is provided that includes a mixture-coated silicon negative electrode of B, O, li, C.
Optionally, the mixture includes Li 3-xCxB1-xO3, where x has a value of 0.1 to 0.5.
Optionally, the silicon negative electrode is a silicon ball or a silicon rod.
Optionally, the mixture further comprises Li 3BO3 and/or LiBO 2;
And/or the mixture is prepared by adopting a gas phase method.
Optionally, the silicon cathode is a silicon sphere, and the diameter of the silicon sphere is 100-500nm.
As another aspect of the embodiments of the present disclosure, there is provided a method for preparing a silicon negative electrode of a battery, including the steps of:
placing the lithium compound in a first temperature control area of a constant temperature reaction container, placing the boride compound in a second temperature control area of the constant temperature reaction container, and placing the silicon ball or the silicon rod in a third temperature control area of the constant temperature reaction container;
Introducing inert gas into the constant temperature reaction vessel, and respectively applying different temperatures to the first temperature control zone, the second temperature control zone and the third temperature control zone to enable the lithium compound and the boride to be coated on the surface of the silicon ball or the silicon rod in a gas phase manner;
switching inert gas into oxygen, and introducing the oxygen into a constant-temperature reaction container, wherein the temperature of a third temperature control area is set to be 200-400 ℃ so that lithium compounds and boride on the surface of a silicon ball or a silicon rod are oxidized into a Li-B-O coating layer;
Switching oxygen into carbon dioxide gas, and introducing the carbon dioxide gas into a constant-temperature reaction container, wherein the temperature of a third temperature control region is set to be 400-800 ℃ so that the Li-B-O coating layer is converted into a Li-B-C-O coating layer.
Optionally, the Li-B-C-O coating layer has a thickness of 2-50nm;
and/or the boride comprises one or more of boron ethoxide, boron isopropoxide, boron trichloride, boron tribromide or boron iodide;
And/or the lithiate comprises one or more of lithium ethoxide, lithium isopropoxide, lithium amide or lithium imide.
As another aspect of an embodiment of the present disclosure, there is provided an all-solid-state sulfide lithium battery including the above-described battery silicon anode.
Optionally, the sulfide all-solid-state lithium battery further comprises a positive electrode material, wherein the positive electrode material is one or more of a Li-Fe-P-O positive electrode, a Li-Ni-Mn-Co-O positive electrode or an S positive electrode.
As another aspect of the embodiments of the present disclosure, there is provided the use of the above-described battery silicon anode in a polymer all-solid-state battery, an oxide all-solid-state battery, or a halide all-solid-state battery.
The method has the beneficial effects that the surface of the traditional nano silicon negative electrode is coated with a layer of nano Li-C-B-O mixture by adopting a gas phase method, and the coating layer has the characteristics of high lithium ion conductivity and the like, and has the characteristics of uniformity, compactness, high lithium ion conductivity, stable low potential and the like. The rate capability and long-cycle stability of the Si negative electrode in the sulfide all-solid-state battery can be improved. Is suitable for commercialized popularization of Si cathodes in sulfide all-solid-state batteries.
Drawings
Fig. 1 shows a schematic diagram of a preparation method of a silicon anode of a battery in example 1.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The particle size of the sulfide electrolyte below may be processed by a ball mill, a sand mill, or an air flow mill. The constant temperature reaction vessel can be a muffle furnace, an oil bath or a constant temperature reaction vessel. Inert containers refer to containers that are filled with an inert gas (nitrogen or argon, etc.) to exclude other gases.
Example 1
Referring to fig. 1, the preparation method of the Li-B-C-O coated battery silicon anode comprises the following steps:
0.2g of lithium ethoxide is placed in the left temperature control area of the tube furnace, 1g of boron iodide is placed in the middle temperature control area of the tube furnace, and 10g of nano silicon spheres is placed in the right temperature control area of the tube furnace. Introducing high-purity argon shielding gas with the gas flow of 0.2L/min, setting the temperature of 80 ℃, 350 ℃ and 25 ℃ respectively from left to right for 1h, switching the high-purity argon into oxygen with the gas flow of 0.2L/min, setting the temperature of the right nano silicon sphere side to 300 ℃ for 3h, and preparing the nano silicon anode (Li-B-O@Si) coated with the Li-B-O nano layer. Continuously switching oxygen into carbon dioxide gas with the gas flow rate of 0.2L/min, setting the temperature of the right side nano silicon sphere side to 600 ℃, and reacting for 3h to convert the Li-B-O nano coating layer into the Li-B-C-O nano coating layer to prepare the nano silicon anode (Li-B-C-O@Si) coated with the Li-B-O nano layer.
Weighing NCM811 and Li 6PS5 Cl solid electrolyte coated by LiNbO 3 according to the mass ratio of 70:27:3, grinding for 10min to prepare the composite anode. 30mg of the composite positive electrode and 120mg of sulfide solid electrolyte were pressed into a positive electrode and electrolyte layer mixed assembly having a diameter of 10 mm.
Weighing the prepared Li-B-C-O@Si mixed anode material and Li 6PS5 Cl solid electrolyte according to the mass ratio of 70:30, and grinding for 10min to prepare the sulfide composite anode. 3mg of the composite negative electrode was pressed at the above positive electrode and electrolyte layer assembly, and an all-solid battery was assembled and subjected to electrochemical performance test. The test conditions are that the current multiplying power is switched between 0.1C-0.3C-0.5C-1C-2C, the voltage range is 3.0-4.3V (vs. Li+/Li), the test pressure is 1MPa, the cycle is 1,100,300 weeks, and the test comparison results are shown in Table 1. Meanwhile, the negative electrode materials are respectively tested by adopting untreated Si nano particles and Li-B-C-O monomer materials as comparison data.
As can be seen from Table 1, compared with the use of untreated Si anode and Li-B-C-O monomer material as anode, the use of Li-B-C-O@Si has a significant improvement in rate capability, while the Li-B-C-O monomer material has no significant lithium intercalation capacity.
TABLE 1
Ps- -represents that the battery fails to work normally and a short circuit occurs
In another aspect of the disclosed embodiments, the silicon negative electrode of the battery is obtained by the preparation method, and the silicon negative electrode comprises a silicon negative electrode coated by a mixture composed of B, O, li, C.
In some embodiments, the B, O, li, C mixture includes Li 3-xCxB1-xO3, where x has a value of 0.1 to 0.5, including, for example, one or more of Li2.9C0.1B0.9 O3、Li2.8C0.2B0.8 O3、Li2.7C0.3B0.7O3、Li2.6C0.4B0.6 O3、Li2.5C0.5B0.5 O3、.
In some embodiments, the mixture further includes one or more of Li 3BO3 or LiBO 2. For example, the mixture includes Li2.9C0.1B0.9O3、Li2.8C0.2B0.8O3、Li3BO3 and LiBO 2, or the mixture includes Li2.8C0.2B0.8O3、Li2.7C0.3B0.7O3、Li2.6C0.4B0.6O3、Li3BO3 and LiBO 2, or the mixture includes Li2.9C0.1B0.9O3、Li2.8C0.2B0.8O3、Li2.7C0.3B0.7O3、Li2.6C0.4B0.6O3、Li2.5C0.5B0.5O3、Li3BO3 and LiBO 2, or the mixture includes Li 2.5C0.5B0.5O3、LiBO3. Those skilled in the art will recognize that the combination of the mixtures is also not limited to combinations of the above materials, but merely gives examples of different combinations.
In some embodiments, the nano silicon spheres in the above embodiments may be replaced by silicon rods, resulting in a silicon rod anode material.
In some embodiments, the lithium ethoxide in the above embodiments may be replaced with a corresponding mass of lithium isopropoxide, and likewise, the boron iodide may be replaced with a corresponding mass of boron trichloride or boron tribromide.
In some embodiments, the silicon sphere diameter can range from 100nm to 500nm, for example, the silicon sphere diameter can be 100nm, 250nm, or 500nm, and can be adjusted as desired.
As another aspect of the presently disclosed embodiments, there is also provided an all-solid-state sulfide lithium battery including the battery silicon anode in the above-described embodiments.
In some embodiments, the lithium battery further includes a positive electrode material, for example, the positive electrode material may be a Li-Fe-P-O-based positive electrode, a Li-Ni-Mn-Co-O-based positive electrode, or an S-positive electrode.
As another aspect of embodiments of the present disclosure, there is provided a use of a silicon negative electrode of a battery, for example, in a polymer all-solid-state battery, an oxide all-solid-state battery, or a halide all-solid-state battery.
Example 2
As an aspect of the present embodiment, the present embodiment provides a method for preparing a Li-B-C-O coated silicon negative electrode for a battery, comprising the steps of:
0.3g of lithium amide or lithium imino is placed in the left side temperature control zone of the tube furnace, 1g of boron ethoxide or boron isopropoxide is placed in the middle temperature control zone of the tube furnace, and 10g of nano silicon spheres or silicon rods are placed in the right side temperature control zone of the tube furnace. Introducing high-purity argon shielding gas with the gas flow of 0.2L/min, setting the temperature of 450 ℃ and 250 ℃ and 25 ℃ respectively from left to right for 1h, switching the high-purity argon into oxygen with the gas flow of 0.2L/min, setting the temperature of the right nano silicon sphere side to 200 ℃ for 3h, and preparing the nano silicon anode (Li-B-O@Si) coated with the Li-B-O nano layer. Continuously switching oxygen into carbon dioxide gas with the gas flow rate of 0.2L/min, setting the temperature of the right side nano silicon sphere side to 400 ℃, and reacting for 3h to convert the Li-B-O nano coating layer into the Li-B-C-O nano coating layer to prepare the nano silicon anode (Li-B-C-O@Si) coated with the Li-B-O nano layer.
Weighing NCM811 and Li 6PS5 Cl solid electrolyte coated by LiNbO 3 according to the mass ratio of 70:27:3, grinding for 10min to prepare the composite anode. 30mg of the composite positive electrode and 120mg of sulfide solid electrolyte were pressed into a positive electrode and electrolyte layer mixed assembly having a diameter of 10 mm.
Weighing the prepared Li-B-C-O@Si mixed anode material and Li 6PS5 Cl solid electrolyte according to the mass ratio of 70:30, and grinding for 10min to prepare the sulfide composite anode. 3mg of the composite negative electrode was pressed at the above positive electrode and electrolyte layer assembly, and an all-solid battery was assembled and subjected to electrochemical performance test. The test conditions are that the current multiplying power is switched between 0.1C-0.3C-0.5C-1C-2C, the voltage range is 3.0-4.3V (vs. Li+/Li), the test pressure is 1MPa, the cycle is 1,100,300 weeks, and the test comparison results are shown in Table 2.
TABLE 2
As another aspect of the embodiments of the present disclosure, there is also provided an all-solid-state sulfide lithium battery including the battery silicon anode in the present embodiment.
In some embodiments, the sulfide all-solid state lithium battery further includes a positive electrode material, for example, the positive electrode material may be a Li-Fe-P-O-based positive electrode, a Li-Ni-Mn-Co-O-based positive electrode, or an S-positive electrode.
As another aspect of the present embodiment, there is also provided an application of the silicon negative electrode of the battery, for example, an application to a polymer all-solid-state battery, an oxide all-solid-state battery, and a halide all-solid-state battery.
Example 3
As an aspect of the present embodiment, the present embodiment provides a method for preparing a Li-B-C-O coated silicon negative electrode for a battery, comprising the steps of:
And (3) placing 0.3g of lithium ethoxide and/or lithium isopropoxide in a left temperature control area of the tubular furnace, placing one or the combination of 1g of boron trichloride, boron tribromide or boron iodide in a middle temperature control area of the tubular furnace, and placing 10g of nano silicon spheres or silicon rods in a right temperature control area of the tubular furnace. Introducing high-purity argon shielding gas with the gas flow of 0.2L/min, setting the temperature of 100 ℃, 200 ℃ and 25 ℃ respectively from left to right for 1h, switching the high-purity argon into oxygen with the gas flow of 0.2L/min, setting the temperature of the right nano silicon sphere side to 400 ℃ for 3h, and preparing the nano silicon anode (Li-B-O@Si) coated with the Li-B-O nano layer. And continuously switching oxygen into carbon dioxide gas, wherein the gas flow is 0.2L/min, and the temperature of the right side nano silicon sphere side is set to 800 ℃ until the Li-B-O nano coating layer is converted into the Li-B-C-O nano coating layer, so as to prepare the nano silicon negative electrode (Li-B-C-O@Si) coated with the Li-B-O nano layer.
Weighing an NCM material (such as NCM 811) coated by LiNbO 3, li 6PS5 Cl solid electrolyte and VGCF conductive carbon according to the mass ratio of 70:27:3, and grinding for 10min to prepare the composite anode. 30mg of the composite positive electrode and 120mg of sulfide solid electrolyte were pressed into a positive electrode and electrolyte layer mixed assembly having a diameter of 10 mm.
Weighing the prepared Li-B-C-O@Si mixed anode material and Li 6PS5 Cl solid electrolyte according to the mass ratio of 70:30, and grinding for 10min to prepare the sulfide composite anode. 3mg of the composite negative electrode was pressed at the above positive electrode and electrolyte layer assembly, and an all-solid battery was assembled and subjected to electrochemical performance test. The test conditions are that the current multiplying power is switched between 0.1C-0.3C-0.5C-1C-2C, the voltage range is 3.0-4.3V (vs. Li+/Li), the test pressure is 1MPa, the cycle is 1,100,300 weeks, and the test comparison results are shown in Table 3.
TABLE 3 Table 3
In some embodiments, lithium ethoxide and/or lithium isopropoxide may also be replaced with a combination of other various lithiates, such as a combination between lithium ethoxide, lithium isopropoxide, lithium amide, or lithium iminoide.
In some embodiments, boron trichloride, boron tribromide, or boron iodide may also be replaced with a combination of other borides, such as a combination between boron ethoxide, boron isopropoxide, boron trichloride, boron tribromide, or boron iodide.
As another aspect of the embodiments of the present disclosure, there is also provided an all-solid-state sulfide lithium battery including the battery silicon anode in the present embodiment.
In some embodiments, the sulfide all-solid state lithium battery further includes a positive electrode material, for example, the positive electrode material may be a Li-Fe-P-O-based positive electrode, a Li-Ni-Mn-Co-O-based positive electrode, or an S-positive electrode.
As another aspect of the present embodiment, there is also provided an application of the silicon negative electrode of the battery, for example, an application to a polymer all-solid-state battery, an oxide all-solid-state battery, and a halide all-solid-state battery.
Although embodiments of the present disclosure have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the disclosure, the scope of which is defined in the appended claims and their equivalents.

Claims (7)

1.一种电池硅负极制备方法，其特征在于，包括如下步骤：1. A method for preparing a silicon negative electrode for a battery, characterized in that it comprises the following steps: 将锂化物置于恒温反应容器第一控温区，硼化物置于恒温反应容器第二控温区，硅球或硅棒置于恒温反应容器内第三控温区；The lithium compound is placed in the first temperature control zone of the constant temperature reaction container, the boride is placed in the second temperature control zone of the constant temperature reaction container, and the silicon ball or silicon rod is placed in the third temperature control zone of the constant temperature reaction container; 向恒温反应容器通入惰性气体，分别对第一控温区、第二控温区和第三控温区施加不同温度，使得锂化物和硼化物气相包覆在硅球或硅棒表面；Inert gas is introduced into the constant temperature reaction container, and different temperatures are applied to the first temperature control zone, the second temperature control zone, and the third temperature control zone, respectively, so that the lithium compound and the boride are coated on the surface of the silicon ball or the silicon rod in the gas phase; 将惰性气体切换为氧气通入恒温反应容器，设置第三控温区温度为200-400℃，使得硅球或硅棒表面的锂化物和硼化物氧化成Li-B-O包覆层；Switch the inert gas to oxygen and pass it into the constant temperature reaction container, set the temperature of the third temperature control zone to 200-400° C., so that the lithium compounds and borides on the surface of the silicon spheres or silicon rods are oxidized into a Li-B-O coating layer; 将氧气切换为二氧化碳气体通入恒温反应容器，设置第三控温区温度为400-800℃，使得Li-B-O包覆层转变为Li-B-C-O包覆层；Switching oxygen to carbon dioxide gas and introducing it into the constant temperature reaction container, setting the temperature of the third temperature control zone to 400-800° C., so that the Li-B-O coating layer is transformed into a Li-B-C-O coating layer; 所述Li-B-C-O包覆层包括LiCxB1-xO3，其中，x取值为0.1-0.5。The Li-BCO coating layer includes LiC x B 1-x O 3, wherein x is 0.1-0.5. 2.如权利要求1所述的电池硅负极制备方法，其特征在于，所述Li-B-C-O包覆层厚度为2-50 nm。2. The method for preparing a battery silicon negative electrode according to claim 1, characterized in that the thickness of the Li-B-C-O coating layer is 2-50 nm. 3.如权利要求1所述的电池硅负极制备方法，其特征在于，所述硼化物包括如下材料中的一种或多种：乙醇硼、异丙醇硼、三氯化硼、三溴化硼或碘化硼。3. The method for preparing a silicon negative electrode for a battery according to claim 1, wherein the boride comprises one or more of the following materials: boron ethanolate, boron isopropoxide, boron trichloride, boron tribromide or boron iodide. 4.如权利要求1所述的电池硅负极制备方法，其特征在于，所述锂化物包括如下材料中的一种或多种：乙醇锂、异丙醇锂、氨基锂或亚氨基锂。4. The method for preparing a silicon negative electrode for a battery according to claim 1, wherein the lithium compound comprises one or more of the following materials: lithium ethoxide, lithium isopropoxide, lithium amide or lithium imide. 5.一种锂电池，包括如权利要求1-4任一项所述的电池硅负极制备方法制备得到的电池硅负极。5. A lithium battery, comprising a battery silicon negative electrode prepared by the method for preparing a battery silicon negative electrode according to any one of claims 1 to 4. 6.如权利要求5所述的锂电池，其特征在于，所述锂电池还包括正极材料，所述正极材料为以下材料中的一种或多种：Li-Fe-P-O系正极、Li-Ni-Mn-Co-O系正极或S正极。6. The lithium battery as claimed in claim 5, characterized in that the lithium battery also includes a positive electrode material, and the positive electrode material is one or more of the following materials: Li-Fe-P-O positive electrode, Li-Ni-Mn-Co-O positive electrode or S positive electrode. 7.一种如权利要求1-4任一项所述的电池硅负极制备方法制备得到的电池硅负极的应用，所述电池硅负极应用在聚合物全固态电池、氧化物全固态电池、硫化物全固态电池或卤化物全固态电池中。7. An application of a battery silicon negative electrode prepared by the battery silicon negative electrode preparation method as described in any one of claims 1 to 4, wherein the battery silicon negative electrode is used in a polymer all-solid-state battery, an oxide all-solid-state battery, a sulfide all-solid-state battery or a halide all-solid-state battery.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111883759A (en) * 2020-07-29 2020-11-03 黄杰 Nano-silicon composite material with core-shell structure and preparation method thereof
CN112864357A (en) * 2019-11-27 2021-05-28 中国科学院上海硅酸盐研究所 Metal borate modified lithium ion battery electrode composite material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201814039D0 (en) * 2018-08-29 2018-10-10 Ilika Tech Ltd Method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112864357A (en) * 2019-11-27 2021-05-28 中国科学院上海硅酸盐研究所 Metal borate modified lithium ion battery electrode composite material and preparation method thereof
CN111883759A (en) * 2020-07-29 2020-11-03 黄杰 Nano-silicon composite material with core-shell structure and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Achieving Both High Ionic Conductivity and High Interfacial Stability with the Li2+xC1−xBxO3 Solid-State Electrolyte: Design from Theoretical Calculations;Bingkai Zhang等;ACS Appl. Mater. Interfaces;20200116;第12卷;第6007−6014页 *

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