CN108321362B - Silicon oxide for negative electrode material of non-aqueous electrolyte secondary battery - Google Patents

Silicon oxide for negative electrode material of non-aqueous electrolyte secondary battery Download PDF

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Publication number
CN108321362B
CN108321362B CN201711385351.9A CN201711385351A CN108321362B CN 108321362 B CN108321362 B CN 108321362B CN 201711385351 A CN201711385351 A CN 201711385351A CN 108321362 B CN108321362 B CN 108321362B
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lithium
silicon oxide
negative electrode
secondary battery
electrolyte secondary
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CN108321362A (en
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廖云龙
杨茂萍
齐美洲
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/36—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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Silicon Compounds (AREA)

Abstract

Disclosed is a silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery, which is a lithium-containing silicon oxide obtained by co-depositing SiO gas and a lithium-containing gas, and the lithium content of the lithium-containing silicon oxide is 0.1-20%. The lithium-containing silicon oxide has excellent performance, can improve the performance of a non-aqueous electrolyte secondary battery, has small volume expansion and excellent cycle performance, and also has excellent performances of high initial coulombic efficiency and high capacity. The invention has the advantages of easily obtained raw materials and low cost, and can be widely applied to industrial production.

Description

Silicon oxide for negative electrode material of non-aqueous electrolyte secondary battery
Technical Field
The invention relates to the technical field of battery materials, in particular to a silicon oxide for a negative electrode material of a non-aqueous electrolyte secondary battery.
Background
As one of the new-generation green energy sources, lithium ion batteries have high energy density and good cycle performance, and are widely used in portable electronic devices, electric vehicle power supplies, and power energy storage systems. The mileage of a traditional internal combustion engine automobile for single energy charging is 600-800km, while the current power lithium ion battery is 200-300km, still has a larger difference. The current commercialized lithium ion battery negative electrode materials mainly adopt graphite, silicon-based negative electrodes and the like. Although the theoretical specific capacity of the silicon-based negative electrode material is several times that of the traditional graphite negative electrode material, the silicon-based negative electrode material has the problem of low first coulombic efficiency. Further improving the performance of the lithium ion battery, and having great significance in researching and developing the silicon-based negative electrode material of the lithium ion battery with high capacity and long cycle performance. Silicon oxide (SiO)xX is an oxide coating film, 0<x<2) Amorphous silicon with a particle size of several to several tens of nanometers is finely dispersed in the silica-like structure. The lithium insertion capacity of the silicon oxide material is 4-6 times that of the graphite material although lower than that of the silicon material, the volume expansion of the silicon oxide material is smaller, the cycle performance is excellent, and the silicon oxide material can be considered as a good negative electrode material; however, the silicon oxide material serving as the lithium ion battery cathode material has low coulombic efficiency for the first time and is recycledThe ring performance is to be improved.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a silicon oxide for a negative electrode material of a non-aqueous electrolyte secondary battery, so as to achieve the purpose of improving the first coulombic efficiency and capacity of the battery.
The invention provides a silicon oxide for a negative electrode material of a non-aqueous electrolyte secondary battery, which is a lithium-containing silicon oxide obtained by co-depositing SiO gas and lithium-containing gas, and the lithium content of the lithium-containing silicon oxide is 0.1-20%.
Preferably, the lithium-containing silicon oxide contains lithium without Li2And (4) carrying out O-formation.
Preferably, the lithium-containing silicon oxide contains 0.5 to 15% of lithium.
Preferably, the lithium-containing silicon oxide has an average particle diameter of 0.1 to 30 μm and a BET specific surface area of 0.5 to 30m2/g。
Preferably, the lithium-containing silicon oxide has an average particle size of 0.2 to 20 μm and a BET specific surface area of 1 to 20m2/g。
Preferably, the raw material of the lithium-containing gas is lithium metal or a lithium-containing compound.
Preferably, the lithium-containing compound is selected from Li2O、Li2CO3And LiOH.
Preferably, the preparation method of the lithium-containing silicon oxide comprises the following specific steps: heating the raw material A to generate SiO gas, supplying lithium-containing gas to the generated SiO gas, and jointly depositing to obtain lithium-containing silicon oxide; wherein the raw material A is a mixture of silicon dioxide powder and silicon powder or silicon oxide powder.
Preferably, the raw material a is heated under reduced pressure or under inert gas conditions.
Preferably, the heating temperature of the raw material A is 1100-1700 ℃.
Preferably, the heating temperature of the raw material A is 1200-1500 ℃.
Preferably, the pressure of the reduced pressure condition is 5 to 100 Pa.
Preferably, the inert gas is selected from one of argon and helium.
Preferably, the deposition temperature is 500-.
Preferably, the deposition temperature is 500-.
Compared with the prior art, the invention has the beneficial effects that:
1) the lithium-containing silicon oxide of the present invention contains 0.1 to 20% of lithium and does not contain Li2O to form a silicon-lithium alloy or Li2SiO3Therefore, the silicon oxide after lithium supplementation has excellent performance, and can be used as a negative electrode material of a non-aqueous electrolyte secondary battery having excellent high-quality performance.
2) The nonaqueous electrolyte secondary battery prepared by the invention has the excellent characteristics of high battery capacity, first coulomb efficiency improved in a step mode and good battery multiplying power performance.
3) The invention has the advantages of easily obtained raw materials and low cost, and can be widely applied to industrial production.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery, which is a lithium-containing silicon oxide obtained by co-depositing SiO gas and a lithium-containing gas, and which contains lithium in an amount of 0.1 to 20%.
Example 2
A silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery, which is a lithium-containing silicon oxide obtained by co-depositing SiO gas and a lithium-containing gas, and which contains 20% of lithium;
wherein the lithium-containing silicon oxide contains lithium without Li2O-forming; the lithium-containing silicon oxide has an average particle diameter of 0.1 [ mu ] m and a BET specific surface area of 30m2(ii)/g; the raw material of the lithium-containing gas is lithium metal;
the preparation method of the lithium-containing silicon oxide comprises the following specific steps: heating the raw material A to 1100 ℃ to generate SiO gas, supplying lithium-containing gas to the generated SiO gas at 1600 ℃, and jointly depositing to obtain lithium-containing silicon oxide, wherein the raw material A is silicon oxide powder;
heating the raw material A under the reduced pressure; the pressure of the reduced pressure environment is 5 Pa.
Example 3
A silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery, which is a lithium-containing silicon oxide obtained by co-depositing SiO gas and a lithium-containing gas, and which contains lithium in an amount of 0.1%;
wherein the lithium-containing silicon oxide contains lithium without Li2O-forming; the lithium-containing silicon oxide has an average particle diameter of 30 [ mu ] m and a BET specific surface area of 0.5m2(ii)/g; the raw material of the lithium-containing gas is a lithium-containing compound; the lithium-containing compound is Li2O and LiOH;
the preparation method of the lithium-containing silicon oxide comprises the following specific steps: heating a raw material A to 1700 ℃ to generate SiO gas, supplying lithium-containing gas to the generated SiO gas at the temperature of 500 ℃, and jointly depositing to obtain lithium-containing silicon oxide, wherein the raw material A is a mixture of silicon dioxide powder and silicon powder;
heating the raw material A under the reduced pressure; the pressure of the reduced pressure environment is 100 Pa.
Example 4
A silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery, which is a lithium-containing silicon oxide obtained by co-depositing SiO gas and a lithium-containing gas, and which contains 15% of lithium;
wherein the lithium-containing silicon oxide contains lithium without Li2O-forming; the lithium-containing silicon oxide has an average particle diameter of 0.2 [ mu ] m and a BET specific surface area of 20m2(ii)/g; the raw material of the lithium-containing gas is a lithium-containing compound; the lithium-containing compound is Li2O；
The preparation method of the lithium-containing silicon oxide comprises the following specific steps: heating the raw material A to 1200 ℃ to generate SiO gas, supplying lithium-containing gas to the generated SiO gas at the temperature of 1000 ℃, and jointly depositing to obtain lithium-containing silicon oxide, wherein the raw material A is silicon oxide powder;
heating the raw material A under the condition of inert gas; the inert gas is argon.
Example 5
A silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery, which is a lithium-containing silicon oxide obtained by co-depositing SiO gas and a lithium-containing gas, and which contains lithium in an amount of 0.5%;
wherein the lithium-containing silicon oxide contains lithium without Li2O-forming; the lithium-containing silicon oxide has an average particle size of 20 μm and a BET specific surface area of 1m2(ii)/g; the raw material of the lithium-containing gas is a lithium-containing compound; the lithium-containing compound is Li2CO3And LiOH;
the preparation method of the lithium-containing silicon oxide comprises the following specific steps: heating a raw material A to 1500 ℃ to generate SiO gas, supplying lithium-containing gas to the generated SiO gas at the temperature of 500 ℃, and jointly depositing to obtain lithium-containing silicon oxide, wherein the raw material A is a mixture of silicon dioxide powder and silicon powder;
heating the raw material A under the condition of inert gas; the inert gas is helium.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (11)

1. A silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery, characterized in that it is a lithium-containing silicon oxide obtained by co-depositing SiO gas and a lithium-containing gas, and the lithium-containing silicon oxide has a lithium content of 0.1 to 0.5%;
the lithium-containing silicon oxide contains lithium-containing Li2O-forming;
the preparation method of the lithium-containing silicon oxide comprises the following specific steps: heating the raw material A to generate SiO gas, supplying lithium-containing gas to the generated SiO gas, and jointly depositing to obtain lithium-containing silicon oxide; wherein the raw material A is a mixture of silicon dioxide powder and silicon powder or silicon oxide powder; the deposition temperature is 1000-1600 ℃.
2. The silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery according to claim 1, wherein a lithium content of the lithium-containing silicon oxide is 0.5%.
3. The silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery according to claim 1, wherein the silicon oxide containing lithium has an average particle diameter of 0.1 to 30 μm and a BET specific surface area of 0.5 to 30m2/g。
4. The silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery according to claim 1, wherein the silicon oxide containing lithium has an average particle diameter of 0.2 to 20 μm and a BET specific surface area of 1 to 20m2/g。
5. The silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery according to claim 1, wherein the raw material of the lithium-containing gas is lithium metal or a lithium-containing compound.
6. The silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery according to claim 5, wherein the lithium-containing compound is selected from Li2O、Li2CO3And LiOH.
7. The silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery according to claim 1, wherein the raw material A is heated under reduced pressure or under an inert gas condition.
8. The silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery according to claim 7, wherein the heating temperature of the raw material A is 1100-1700 ℃.
9. The silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery according to claim 7, wherein the heating temperature of the raw material A is 1200-1500 ℃.
10. The silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery according to claim 7, wherein the pressure under the decompression condition is 5 to 100 Pa.
11. The silicon oxide for a negative electrode material of a nonaqueous electrolyte secondary battery according to claim 7, wherein the inert gas is one selected from argon gas and helium gas.
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KR20190029711A (en) 2016-10-19 2019-03-20 오사카 티타늄 테크놀로지스 캄파니 리미티드 Silicon oxide-based anode material and manufacturing method thereof
CN111900366B (en) * 2020-07-02 2023-01-06 有研资源环境技术研究院(北京)有限公司 SiO containing lithium x Method for preparing powder

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1188335A (en) * 1996-11-29 1998-07-22 精工电子有限公司 Non-aqueous electrolyte secondary battery
CN102255082A (en) * 2010-05-21 2011-11-23 信越化学工业株式会社 Silicon oxide material, making method, negative electrode, lithium ion secondary battery, and electrochemical capacitor
CN103857623A (en) * 2011-10-14 2014-06-11 信越化学工业株式会社 Silicon oxide for negative electrode material of nonaqueous electroltye secondary cell, method for producing same, lithium ion secondary cell, and electrochemical capacitor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1188335A (en) * 1996-11-29 1998-07-22 精工电子有限公司 Non-aqueous electrolyte secondary battery
CN102255082A (en) * 2010-05-21 2011-11-23 信越化学工业株式会社 Silicon oxide material, making method, negative electrode, lithium ion secondary battery, and electrochemical capacitor
CN103857623A (en) * 2011-10-14 2014-06-11 信越化学工业株式会社 Silicon oxide for negative electrode material of nonaqueous electroltye secondary cell, method for producing same, lithium ion secondary cell, and electrochemical capacitor

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