CN114835131A - Preparation method of lithium silicate cathode material and lithium ion battery - Google Patents

Preparation method of lithium silicate cathode material and lithium ion battery Download PDF

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Publication number
CN114835131A
CN114835131A CN202210276987.4A CN202210276987A CN114835131A CN 114835131 A CN114835131 A CN 114835131A CN 202210276987 A CN202210276987 A CN 202210276987A CN 114835131 A CN114835131 A CN 114835131A
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lithium
preparation
powder
lithium silicate
sio
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高峰
赵冬梅
张要枫
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Hubei Titanium Era New Energy Co Ltd
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Hubei Titanium Era New Energy Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/32—Alkali metal silicates
    • 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
    • H01M4/58—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The application discloses a preparation method of a lithium silicate anode material and a lithium ion battery. The preparation method of the lithium silicate anode material comprises the following steps: A. providing SiO powder; B. carrying out dry ball milling on SiO powder and lithium metal powder to obtain a first intermediate containing a silicon lithium compound and lithium silicate; C. carrying out lithium removal reaction on the first intermediate to obtain a second intermediate containing a silicon simple substance and lithium silicate; D. and calcining the second intermediate to obtain the lithium silicate anode material. According to the preparation method, the SiO powder and the metal Li powder are mixed and ball-milled to realize uniform mixing of the two substances, and the particle size is uniform. Moreover, the low molecular weight hydrocarbon gas is introduced in the calcining process, so that the forming of the lithium silicate anode material is promoted. The negative electrode material obtained by the preparation method is assembled in a battery, the mass ratio of 0.2C capacity to 1600mAh/g and 1C capacity to 1600mAh/g obviously shows that the lithium ion battery silicon-carbon composite negative electrode material has good first efficiency and rate capability.

Description

Preparation method of lithium silicate cathode material and lithium ion battery
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a preparation method of a lithium silicate negative electrode material and a lithium ion battery.
Background
Currently, lithium ion batteries are widely used in our market, such as: the method is also applied to the fields of new energy automobiles, energy storage power stations, mobile communication mobile phones, notebook computers and the like in depth in the fields of military, aerospace and the like. The requirement of consumers on endurance mileage is higher and higher, the weight reduction of 3C products is also emphasized more and more, the current carbon negative electrodes such as graphite, hard carbon, soft carbon, mesocarbon microbeads and the like cannot meet the requirements of consumers, but the gram capacity of the current conventional silicon oxide and silicon carbide materials can meet the basic requirement, but the poor cycle caused by volume expansion is a ubiquitous problem in the industry, so the negative electrode material with high specific capacity and long cycle is in urgent need of development and application.
In the related art, the preparation method of the lithium silicate anode material has poor electrochemical performance.
Disclosure of Invention
In view of this, the present application provides a method for preparing a lithium silicate negative electrode material, which can effectively improve the electrochemical performance of the prepared lithium silicate negative electrode material.
In a first aspect, the present application provides a method for preparing a lithium silicate anode material, comprising:
A. providing SiO powder;
B. carrying out dry ball milling on the SiO powder and the lithium metal powder to obtain a first intermediate containing a silicon lithium compound and lithium silicate;
C. carrying out lithium removal reaction on the first intermediate to obtain a second intermediate containing a silicon simple substance and lithium silicate;
D. and calcining the second intermediate to obtain the lithium silicate anode material.
Optionally, the SiO powder is obtained in the following manner: and carrying out wet ball milling on the silicon oxide, and then drying.
Optionally, the solvent for wet ball milling and the solvent for desorption reaction are one or more of ethanol, n-propanol and isopropanol, and preferably the volume ratio is 9:1 ethanol, n-propanol.
Optionally, the rotation speed of the wet ball milling is 2000-3000 rpm/min, and the ball milling is carried out until the particle size is less than 5 μm;
preferably, the rotation speed of the dry ball milling is 3000-5000 rpm/min, and the ball milling is carried out until the particle size is less than 4 μm.
Optionally, the mass ratio of the SiO powder to the metallic Li powder is 0.7-0.9: 0.1 to 0.3;
preferably, the first intermediate is a mixture of a first intermediate and a second intermediate, wherein the mass ratio of the first intermediate to the second intermediate is 1.0-1.5: 99.1 to 98.5 of Li 4.4 Si and Li 4 SiO 4 A mixture of (a).
Optionally, the lithium removal reaction is carried out under the condition of adding graphite, and the adding amount of the graphite is 2.5-3.5% of the total mass;
preferably, the lithium removing agent for the lithium removing reaction is ethanol, and the addition amount of the lithium removing agent is 30-55% of the total mass.
Optionally, the second intermediate is a mixture containing a mass ratio of 0.5 to 1.5: 96-98 amorphous Si and porous Li 4 SiO 4 A mixture of (a).
Optionally, the calcination is carried out with the introduction of C ≦4 Preferably in a volume ratio of 7: 3, and 3, a mixed gas of methane and ethane.
Optionally, the sintering temperature is 600-950 ℃, and the sintering time is 2-3 h.
In a second aspect, the present application provides a lithium ion battery containing the negative electrode material obtained by the preparation method as described above.
The two substances are uniformly mixed through mixing and ball-milling of SiO powder and metal Li powder, and the particle size is uniform. Moreover, the low molecular weight hydrocarbon gas is introduced in the calcining process, so that the formation of the lithium silicate anode material is promoted. The negative electrode material obtained by the preparation method is assembled in a battery, the mass ratio of 0.2C capacity to 1600mAh/g and 1C capacity to 1600mAh/g obviously shows that the lithium ion battery silicon-carbon composite negative electrode material has good first efficiency and rate capability.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
< sources of raw materials >
The starting materials used hereinafter are all commercially available.
< procedure of example >
Example 1
(1) Uniformly mixing D50 in a mixed solvent of silicon oxide with the particle size of 30-85 mu m, ethanol and isopropanol with the volume ratio of 9:1, performing wet ball milling in an air atmosphere, and drying to obtain SiO powder with the particle size of less than 1 mu m;
(2) mixing SiO powder and metal Li powder in a mass ratio of 0.85: 0.15, and then the mixture is ball-milled in an Ar gas atmosphere by a dry method to obtain the Li with the mass fraction of 1.1 percent 4.4 Si and 98.9% Li by mass fraction 4.4 Si：Li 4 SiO 4 The two-phase mixture of (a);
(3) adding the two-phase mixture obtained in the step (2) into a lithium removal reaction kettle, adding graphite accounting for 3% of the mass fraction of the two-phase mixture, excessive solvent (mixed solvent with the volume ratio of ethanol to isopropanol being 9: 1) and lithium removal agent, and performing lithium removal reaction for 10 hours to obtain a product (the product CH) 3 CH 2 OLi, amorphous Si, porous Li 4 SiO 4 ) Filtering to obtain amorphous Si and porous Li 4 SiO 4 Wherein the amorphous Si content is 1% by mass, porous Li 4 SiO 4 The mass content of (A) is 97%;
(4) amorphous Si and porous Li 4 SiO 4 In an Ar atmosphere, introducing CH 4 And C 2 H 8 Mixed gas of (2), CH 4 And C 2 H 6 Volume fraction of (d) 70%: 30 percent, and the flow rate of the gas is 600ml/min), and sintering is carried out for 2h at 800 ℃ to obtain the lithium silicate cathode material.
Example 2
The procedure of step (1) was the same as in example 1 except that the solvent was isopropanol, whereby SiO powder was obtained.
The same process steps as in steps (2), (3), and (4) of example 1 were carried out using the SiO powder prepared in example 1 to obtain a lithium silicate negative electrode material.
Example 3
The method of step (1) is the same as example 1, only the solvent is ethanol, and the properties of the obtained SiO powder are good;
the same process steps as in steps (2), (3), and (4) of example 1 were carried out using the SiO powder prepared in example 1 to obtain a lithium silicate negative electrode material.
Example 4
The method of step (1) is the same as example 1, only the solvent is ethanol, and the properties of the obtained SiO powder are good;
the same process steps as in steps (2), (3), and (4) of example 1 were carried out using the SiO powder prepared in example 1 to obtain a lithium silicate negative electrode material.
Example 5
Only different from example 1, in step (2), SiO powder and metallic Li powder were mixed in a mass ratio of 0.75: 0.25.
example 6
Only different from example 1, in step (2), SiO powder and metallic Li powder were mixed in a mass ratio of 0.8: 0.2.
example 7
Only different from example 1, in step (2), SiO powder and metallic Li powder were mixed in a mass ratio of 0.89: 0.11.
example 8
The only difference from example 1 is that step (4) does not add CH 4 And C 2 H 6 The mixed gas of (1).
< evaluation >
1. Evaluation procedure
The lithium silicate carbon negative electrode materials of examples 1 to 4 were used as negative electrode materials, and mixed with polyvinylidene fluoride PVDF as a binder and Super-P as a conductive agent in a ratio of 85: 10: 5, adding a proper amount of N-methyl pyrrolidone, and using a three-component mixed solvent EC of lmol/L LiPF: DMC: EMC 1: 1: the CR2016 simulated battery is assembled by taking the 1, v/v solution as electrolyte and the polypropylene microporous membrane as a diaphragm. In the cycle performance test, a constant current charge and discharge experiment is carried out by using a current of 30mA, and the charge and discharge voltage is limited to 0-1.5V. The electrochemical performance of the experimental battery made of the material of the example was tested by a Land battery test system of Wuhanjinnuo electronics Co.
2. Evaluation results
Figure BDA0003556202070000061
As can be seen from the above table, the electrochemical performance of example 1 is better than that of example 8, i.e. the technical contribution of the alkane gas introduced during the calcination process to the electrochemical performance is proved;
the experimental battery is made of the material prepared in the above table embodiment, the 0.2C discharge capacity is larger than 1600mAh/g, which shows that the lithium ion battery silicon-carbon composite negative electrode material has good first efficiency and rate capability, and is subjected to cycle test.
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 changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (10)

1. A preparation method of a lithium silicate anode material is characterized by comprising the following steps:
A. providing SiO powder;
B. carrying out dry ball milling on the SiO powder and the lithium metal powder to obtain a first intermediate containing a silicon lithium compound and lithium silicate;
C. carrying out lithium removal reaction on the first intermediate to obtain a second intermediate containing a silicon simple substance and lithium silicate;
D. and calcining the second intermediate to obtain the lithium silicate anode material.
2. The method according to claim 1, wherein the SiO powder is obtained by: and carrying out wet ball milling on the silicon oxide, and then drying.
3. The preparation method according to claim 2, wherein the solvent for wet ball milling and the solvent for the desorption reaction are one or more of ethanol, n-propanol and isopropanol, and preferably the volume ratio of the ethanol to the n-propanol to the isopropanol is 9:1 ethanol, n-propanol.
4. The preparation method of the high-performance ball mill is characterized in that the rotation speed of the wet ball mill is 2000-3000 rpm/min, and the ball mill is carried out until the particle size is less than 5 μm;
preferably, the rotation speed of the dry ball milling is 3000-5000 rpm/min, and the ball milling is carried out until the particle size is less than 4 μm.
5. The production method according to claim 1, wherein the mass ratio of the SiO powder to the metallic Li powder is 0.7 to 0.9: 0.1 to 0.3;
preferably, the first intermediate is a mixture of a first intermediate and a second intermediate, wherein the mass ratio of the first intermediate to the second intermediate is 1.0-1.5: 99.1 to 98.5 of Li 4.4 Si and Li 4 SiO 4 A mixture of (a).
6. The preparation method according to claim 5, wherein the delithiation reaction is carried out under the condition of adding graphite, and the adding amount of the graphite is 2.5-3.5% of the total mass;
preferably, the lithium removing agent for the lithium removing reaction is ethanol, and the addition amount of the lithium removing agent is 30-55% of the total mass.
7. The method according to claim 1, wherein the second intermediate is a mixture of a first intermediate and a second intermediate, wherein the second intermediate comprises a mixture of, by mass, 0.5 to 1.5: 96-98 amorphous Si and porous Li 4 SiO 4 A mixture of (a).
8. The method of claim 1, wherein the calcining is carried out by introducing C ≦4 Preferably in a volume ratio of 7: 3, and 3, mixed gas of methane and ethane.
9. The preparation method according to claim 1, wherein the sintering temperature is 600-950 ℃ and the sintering time is 2-3 h.
10. A lithium ion battery comprising the negative electrode material obtained by the production method according to any one of claims 1 to 9.
CN202210276987.4A 2022-03-21 2022-03-21 Preparation method of lithium silicate cathode material and lithium ion battery Pending CN114835131A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1850597A (en) * 2006-04-28 2006-10-25 中国科学院上海硅酸盐研究所 Method for preparig lithium secondary cell silicon/rich-lithium phase composite cathode material by high energy ball milling
CN101789506A (en) * 2009-01-22 2010-07-28 中国科学院上海硅酸盐研究所 Composite cathode material for lithium ion battery and preparation method thereof
CN107534136A (en) * 2015-03-02 2018-01-02 Eo细胞有限公司 With being embedded in silicon：The silica SiClx lithium composite materials and its manufacture method of silicon nanoparticle in silicon lithium silicates composite matrix
CN109923706A (en) * 2016-09-02 2019-06-21 香港商Eo细胞有限公司 With insertion silicon: the silicon-silicon oxide-lithium composite material of the silicon nanoparticle volume change compensation of silicic acid silicon lithium complex matrix, and periodical ex situ manufacturing method
JP2021051904A (en) * 2019-09-25 2021-04-01 株式会社大阪チタニウムテクノロジーズ Method for manufacturing silicon-oxide-based negative electrode material
WO2022001880A1 (en) * 2020-06-28 2022-01-06 贝特瑞新材料集团股份有限公司 Silicon-oxygen composite negative electrode material, negative electrode, lithium ion battery and preparation method therefor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1850597A (en) * 2006-04-28 2006-10-25 中国科学院上海硅酸盐研究所 Method for preparig lithium secondary cell silicon/rich-lithium phase composite cathode material by high energy ball milling
CN101789506A (en) * 2009-01-22 2010-07-28 中国科学院上海硅酸盐研究所 Composite cathode material for lithium ion battery and preparation method thereof
CN107534136A (en) * 2015-03-02 2018-01-02 Eo细胞有限公司 With being embedded in silicon：The silica SiClx lithium composite materials and its manufacture method of silicon nanoparticle in silicon lithium silicates composite matrix
CN109923706A (en) * 2016-09-02 2019-06-21 香港商Eo细胞有限公司 With insertion silicon: the silicon-silicon oxide-lithium composite material of the silicon nanoparticle volume change compensation of silicic acid silicon lithium complex matrix, and periodical ex situ manufacturing method
JP2021051904A (en) * 2019-09-25 2021-04-01 株式会社大阪チタニウムテクノロジーズ Method for manufacturing silicon-oxide-based negative electrode material
WO2022001880A1 (en) * 2020-06-28 2022-01-06 贝特瑞新材料集团股份有限公司 Silicon-oxygen composite negative electrode material, negative electrode, lithium ion battery and preparation method therefor

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