CN108321362A - A kind of non-aqueous electrolyte secondary cell negative electrode material Si oxide - Google Patents

A kind of non-aqueous electrolyte secondary cell negative electrode material Si oxide Download PDF

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Publication number
CN108321362A
CN108321362A CN201711385351.9A CN201711385351A CN108321362A CN 108321362 A CN108321362 A CN 108321362A CN 201711385351 A CN201711385351 A CN 201711385351A CN 108321362 A CN108321362 A CN 108321362A
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Prior art keywords
oxide
lithium
containing lithium
aqueous electrolyte
electrolyte secondary
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CN201711385351.9A
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CN108321362B (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)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Silicon Compounds (AREA)

Abstract

It is the Si oxide containing lithium obtained by keeping SiO gases and gas containing lithium co-deposited, and the amount containing lithium of the Si oxide containing lithium is 0.1 20% the invention discloses a kind of non-aqueous electrolyte secondary cell negative electrode material Si oxide.Present invention Si oxide containing lithium is had excellent performance, and the performance of non-aqueous electrolyte secondary battery can be improved, and volume expansion is smaller, cycle performance is more excellent, also has the excellent properties of high coulombic efficiency, high power capacity for the first time.Raw material of the present invention is easy to get, of low cost, can be widely applied to industrialized production.

Description

A kind of non-aqueous electrolyte secondary cell negative electrode material Si oxide
Technical field
The present invention relates to battery material technical fields, and in particular to a kind of non-aqueous electrolyte secondary cell negative electrode material silicon Oxide.
Background technology
One of green energy resource as a new generation, lithium ion battery possesses high-energy density and good cycle performance, quilt It is widely used in portable electronic device, electric car power supply and electric energy storing system.Traditional combustion engine automobile single fills energy Mileage travelled is 600-800km, and current driving force lithium ion battery is 200-300km, however it remains larger gap.Current commercial The lithium ion battery negative material of change mainly uses graphite, silicon-based anode etc..Although the theoretical specific capacity of silicon based anode material is Several times of conventional graphite negative material, but face lower coulombic efficiency problem for the first time.Further promote lithium ion battery Can, the Silicon Based Anode Materials for Lithium-Ion Batteries for researching and developing large capacity and long circulating performance is of great significance.Si oxide (SiOx, x For aoxidize cover film, 0<x<2) grain size of material is the non-crystalline silicon fine dispersion of several nanometers to several tens of nanometers in class silica knot In structure.Though the embedding lithium capacity of silicon oxide material is low compared with silicon materials, but 4-6 times of graphite material, and its volume expansion Smaller, cycle performance is more excellent, it is contemplated that as good negative material；However silicon oxide material is as lithium ion battery Negative material, coulombic efficiency is relatively low for the first time, and cycle performance is to be improved.
Invention content
Technical problems based on background technology, the present invention propose a kind of non-aqueous electrolyte secondary cell negative electrode material With Si oxide, to realize the purpose for improving battery coulombic efficiency, capacity for the first time.
A kind of non-aqueous electrolyte secondary cell negative electrode material Si oxide proposed by the present invention, is by making SiO gas The Si oxide containing lithium that body and gas containing lithium are co-deposited and obtain, and the amount containing lithium of the Si oxide containing lithium is 0.1- 20%.
Preferably, the non-Li of lithium contained by the Si oxide containing lithium2Oization.
Preferably, the amount containing lithium of the Si oxide containing lithium is 0.5-15%.
Preferably, the average grain diameter of the Si oxide containing lithium is 0.1-30 μm, BET specific surface area 0.5-30m2/g。
Preferably, the average grain diameter of the Si oxide containing lithium is 0.2-20 μm, BET specific surface area 1-20m2/g。
Preferably, the raw material of the gas containing lithium is lithium metal or lithium-containing compound.
Preferably, the lithium-containing compound is selected from Li2O、Li2CO3, at least one of LiOH.
Preferably, the preparation method of the Si oxide containing lithium is as follows：Raw material A is heated, to generate SiO gases supply gas containing lithium to generated SiO gases, and co-deposition obtains Si oxide containing lithium；Wherein, raw material A is oxygen The mixture of SiClx powder or SiO 2 powder and silicon metal powder.
Preferably, the raw material A is heated under decompression or inert gas conditions.
Preferably, the heating temperature of the raw material A is 1100-1700 DEG C.
Preferably, the heating temperature of the raw material A is 1200-1500 DEG C.
Preferably, the pressure of the reduced pressure atmosphere is 5-100Pa.
Preferably, the one kind of the inert gas in argon gas, helium.
Preferably, the depositing temperature is 500-1600 DEG C.
Preferably, the depositing temperature is 500-1000 DEG C.
Compared with prior art, the beneficial effects of the present invention are：
1) the not Li of 0.1~20% lithium contained by Si oxide containing lithium of the invention2Oization, but formed silicon lithium alloy or Li2SiO3Form, therefore the Si oxide mended after lithium is had excellent performance, it can be as the nonaqueous electrolyte of high-quality haveing excellent performance Secondary battery cathode material.
2) non-aqueous electrolyte secondary battery prepared using the present invention, the library for the first time promoted with high battery capacity, ladder The excellent specific property of human relations efficiency, battery high rate performance are good.
3) raw material of the present invention is easy to get, of low cost, can be widely applied to industrialized production.
Specific implementation mode
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of non-aqueous electrolyte secondary cell negative electrode material Si oxide is by making SiO gases and gas containing lithium Co-deposited and acquisition Si oxide containing lithium, and the amount containing lithium of the Si oxide containing lithium is 0.1-20%.
Embodiment 2
A kind of non-aqueous electrolyte secondary cell negative electrode material Si oxide is by making SiO gases and gas containing lithium Co-deposited and acquisition Si oxide containing lithium, and the amount containing lithium of the Si oxide containing lithium is 20%；
Wherein, the non-Li of lithium contained by the Si oxide containing lithium2Oization；The average grain diameter of the Si oxide containing lithium is 0.1 μm, BET specific surface area 30m2/g；The raw material of the gas containing lithium is lithium metal；
The preparation method of the Si oxide containing lithium is as follows：1100 DEG C are heated to raw material A, to generate SiO Gas supplies gas containing lithium at a temperature of 1600 DEG C to generated SiO gases, and co-deposition obtains Si oxide containing lithium, In, raw material A is silicon oxide powder；
The raw material A is performed under reduced pressure heating；The pressure of the reduced pressure atmosphere is 5Pa.
Embodiment 3
A kind of non-aqueous electrolyte secondary cell negative electrode material Si oxide is by making SiO gases and gas containing lithium Co-deposited and acquisition Si oxide containing lithium, and the amount containing lithium of the Si oxide containing lithium is 0.1%；
Wherein, the non-Li of lithium contained by the Si oxide containing lithium2Oization；The average grain diameter of the Si oxide containing lithium is 30 μ M, BET specific surface area 0.5m2/g；The raw material of the gas containing lithium is lithium-containing compound；The lithium-containing compound is Li2O and LiOH；
The preparation method of the Si oxide containing lithium is as follows：1700 DEG C are heated to raw material A, to generate SiO Gas supplies gas containing lithium at a temperature of 500 DEG C to generated SiO gases, and co-deposition obtains Si oxide containing lithium, In, raw material A is the mixture of SiO 2 powder and silicon metal powder；
The raw material A is performed under reduced pressure heating；The pressure of the reduced pressure atmosphere is 100Pa.
Embodiment 4
A kind of non-aqueous electrolyte secondary cell negative electrode material Si oxide is by making SiO gases and gas containing lithium Co-deposited and acquisition Si oxide containing lithium, and the amount containing lithium of the Si oxide containing lithium is 15%；
Wherein, the non-Li of lithium contained by the Si oxide containing lithium2Oization；The average grain diameter of the Si oxide containing lithium is 0.2 μm, BET specific surface area 20m2/g；The raw material of the gas containing lithium is lithium-containing compound；The lithium-containing compound is Li2O；
The preparation method of the Si oxide containing lithium is as follows：1200 DEG C are heated to raw material A, to generate SiO Gas supplies gas containing lithium at being 1000 DEG C in temperature to generated SiO gases, and co-deposition obtains Si oxide containing lithium, Wherein, raw material A is silicon oxide powder；
The raw material A is heated under inert gas conditions；The inert gas is argon gas.
Embodiment 5
A kind of non-aqueous electrolyte secondary cell negative electrode material Si oxide is by making SiO gases and gas containing lithium Co-deposited and acquisition Si oxide containing lithium, and the amount containing lithium of the Si oxide containing lithium is 0.5%；
Wherein, the non-Li of lithium contained by the Si oxide containing lithium2Oization；The average grain diameter of the Si oxide containing lithium is 20 μ M, BET specific surface area 1m2/g；The raw material of the gas containing lithium is lithium-containing compound；The lithium-containing compound is Li2CO3With LiOH；
The preparation method of the Si oxide containing lithium is as follows：1500 DEG C are heated to raw material A, to generate SiO Gas supplies gas containing lithium at being 500 DEG C in temperature to generated SiO gases, and co-deposition obtains Si oxide containing lithium, In, raw material A is the mixture of SiO 2 powder and silicon metal powder；
The raw material A is heated under inert gas conditions；The inert gas is helium.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.

Claims (10)

1. a kind of non-aqueous electrolyte secondary cell negative electrode material Si oxide, which is characterized in that its be by make SiO gases and The Si oxide containing lithium that gas containing lithium is co-deposited and obtains, and the amount containing lithium of the Si oxide containing lithium is 0.1-20%.
2. non-aqueous electrolyte secondary cell negative electrode material Si oxide according to claim 1, which is characterized in that described to contain The non-Li of lithium contained by lithium Si oxide2Oization.
3. non-aqueous electrolyte secondary cell negative electrode material Si oxide according to claim 1, which is characterized in that described to contain The amount containing lithium of lithium Si oxide is 0.5-15%.
4. non-aqueous electrolyte secondary cell negative electrode material Si oxide according to claim 1, which is characterized in that described to contain The average grain diameter of lithium Si oxide is 0.1-30 μm, BET specific surface area 0.5-30m2/g；Preferably, the oxidation of silicon containing lithium The average grain diameter of object is 0.2-20 μm, BET specific surface area 1-20m2/g。
5. non-aqueous electrolyte secondary cell negative electrode material Si oxide according to claim 1, which is characterized in that described to contain The raw material of lithium gas is lithium metal or lithium-containing compound.
6. non-aqueous electrolyte secondary cell negative electrode material Si oxide according to claim 5, which is characterized in that described to contain Lithium compound is selected from Li2O、Li2CO3, at least one of LiOH.
7. non-aqueous electrolyte secondary cell negative electrode material Si oxide according to claim 1, which is characterized in that described to contain The preparation method of lithium Si oxide is as follows：Raw material A is heated, to generate SiO gases, to generated SiO Gas supplies gas containing lithium, and co-deposition obtains Si oxide containing lithium；Wherein, raw material A is silicon oxide powder or silicon dioxide powder The mixture at end and silicon metal powder.
8. non-aqueous electrolyte secondary cell negative electrode material Si oxide according to claim 7, which is characterized in that the original Material A is heated under decompression or inert gas conditions；Preferably, the heating temperature of the raw material A is 1100-1700 DEG C；It is excellent The heating temperature of selection of land, the raw material A is 1200-1500 DEG C.
9. non-aqueous electrolyte secondary cell negative electrode material Si oxide according to claim 8, which is characterized in that described to subtract The pressure in pressure ring border is 5-100Pa；Preferably, the one kind of the inert gas in argon gas, helium.
10. non-aqueous electrolyte secondary cell negative electrode material Si oxide according to claim 7, which is characterized in that described Depositing temperature is 500-1600 DEG C；Preferably, the depositing temperature is 500-1000 DEG C.
CN201711385351.9A 2017-12-20 2017-12-20 Silicon oxide for negative electrode material of non-aqueous electrolyte secondary battery Active CN108321362B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111900366A (en) * 2020-07-02 2020-11-06 有研资源环境技术研究院(北京)有限公司 SiO containing lithiumxMethod for preparing powder
US11031592B2 (en) * 2016-10-19 2021-06-08 Osaka Titanium Technologies Co., Ltd. Lithium doped silicon oxide-based negative electrode material and method of manufacturing the same

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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11031592B2 (en) * 2016-10-19 2021-06-08 Osaka Titanium Technologies Co., Ltd. Lithium doped silicon oxide-based negative electrode material and method of manufacturing the same
US11728479B2 (en) 2016-10-19 2023-08-15 Osaka Titanium Technologies Co., Ltd. Lithium doped silicon oxide-based negative electrode material and method of manufacturing the same
CN111900366A (en) * 2020-07-02 2020-11-06 有研资源环境技术研究院(北京)有限公司 SiO containing lithiumxMethod for preparing powder

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