CN112133898A - Silicon-based negative electrode material and preparation method thereof - Google Patents

Silicon-based negative electrode material and preparation method thereof Download PDF

Info

Publication number
CN112133898A
CN112133898A CN202010997891.8A CN202010997891A CN112133898A CN 112133898 A CN112133898 A CN 112133898A CN 202010997891 A CN202010997891 A CN 202010997891A CN 112133898 A CN112133898 A CN 112133898A
Authority
CN
China
Prior art keywords
silicon
sio
porous
negative electrode
anode material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010997891.8A
Other languages
Chinese (zh)
Other versions
CN112133898B (en
Inventor
王夏阳
曹新龙
田占元
张长安
曹国林
白杨芝
薛孟尧
胥鑫
霍林智
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi Coal and Chemical Technology Institute Co Ltd
Original Assignee
Shaanxi Coal and Chemical Technology Institute Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi Coal and Chemical Technology Institute Co Ltd filed Critical Shaanxi Coal and Chemical Technology Institute Co Ltd
Priority to CN202010997891.8A priority Critical patent/CN112133898B/en
Publication of CN112133898A publication Critical patent/CN112133898A/en
Application granted granted Critical
Publication of CN112133898B publication Critical patent/CN112133898B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/023—Preparation by reduction of silica or free silica-containing material
    • 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
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • 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
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 invention discloses a silicon-based negative electrode material and a preparation method thereofx/Si/Li2OyThe shell of the composite is a carbon coating layer; said pluralityThe hole intermediate layer takes diatomite as a silicon source, wherein x is more than or equal to 1 and less than or equal to 2, and y is more than or equal to 3 and less than or equal to 5; the invention aims to solve the problem of expansion of the silicon-based negative electrode material, improve the first coulombic effect of the material on the basis of not reducing the conductivity, and simultaneously reduce the preparation cost of the material by taking the diatomite as a silicon source, thereby being beneficial to realizing the industrial production of the silicon-based negative electrode material.

Description

Silicon-based negative electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a silicon-based cathode material.
Background
The improvement of energy density is always the main melody of the technical development of the lithium ion battery, and one is to optimize the battery structure, such as the concepts of Ningde time CPT technology, BYD 'blade battery' and the like; another effort is to break through the technical barriers of high capacity materials, which is also the mainstream approach currently taken by battery manufacturers. The anode and cathode materials are the key for improving the energy density of the lithium ion battery, although the anode material occupies a core position in the battery, the theoretical gram capacity of the graphite cathode material is 372mAh/g, which becomes a limiting condition for further improving the energy of the battery, and the silicon-based composite material has higher specific capacity and lower de-intercalation lithium potential and is considered as a new generation of lithium battery cathode material with the most potential.
In order to improve the cycling stability of a silicon-based negative electrode material, the silicon material is generally subjected to nanocrystallization, and the main research directions are as follows: silicon nanoparticles, silicon nanowires, silicon thin films, 3D porous silicon and the like, but the preparation technology of the nanoparticles with complex structures, the one-dimensional nanowires and the like is difficult, the process is complex and the cost is high.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a silicon-based negative electrode material and a preparation method thereof, which solve the problem of expansion of the silicon-based negative electrode material, improve the first coulombic effect of the silicon-based negative electrode material on the basis of not reducing the conductivity, and improve the cycling stability of the silicon-based negative electrode material; meanwhile, the diatomite is used as a silicon source, so that the preparation cost of the material is reduced, and the industrial production of the silicon-based negative electrode material is favorably realized.
In order to achieve the purpose, the invention provides the following technical scheme: the silicon-based negative electrode material comprises a core, a porous middle layer and a shell, wherein the core is a carbon matrix material, and the porous middle layer is SiOx/Si/Li2OyThe shell of the composite is a carbon coating layer; the porous middle layer takes diatomite as a silicon source, wherein x is more than or equal to 1 and less than or equal to 2, and y is more than or equal to 3 and less than or equal to 5.
Further, the carbon matrix material is in a laminar or linear shape, the carbon matrix material is at least one of natural graphite, artificial graphite, soft carbon and hard carbon, and the natural graphite is flake graphite.
The invention also provides a preparation method of the silicon-based negative electrode material, which comprises the following steps:
step one, diatomite is pretreated to obtain purified porous SiO2Powder;
step two, the porous SiO obtained in the step one2Mixing the powder with lithium powder, and carrying out heat treatment in inert atmosphere to obtain porous SiOx/Si/Li2SiOyA complex;
step three, the porous SiO obtained in the step twox/Si/Li2SiOyAnd dispersing the compound, the carbon matrix material and the dispersing agent in a solvent, and carrying out wet grinding to obtain precursor slurry with uniform dispersion.
And step four, performing spray drying, fusion and granulation on the precursor slurry obtained in the step three, and then performing high-temperature carbonization and gas phase coating to finally obtain the silicon-based negative electrode material.
Further, the algae in the first stepThe soil pretreatment is specifically operated as follows: heat treating diatomite to eliminate organic matter, crushing, acid washing, water washing, stoving and crushing to obtain purified porous SiO2Powder; the heating temperature of the heat treatment is 400-750 ℃, and the heat preservation is carried out for 1-4 h; the acid washing is carried out for 1h-4h at 70-100 ℃ by adopting sulfuric acid with the mass fraction of more than 70 percent and the liquid-solid ratio of (2-5) to 1; the acid wash and water wash are alternated until the pH of the wash is between 6 and 8.
Further, in the second step, the lithium powder and SiO2The mass ratio of the powder is 1 (0.5-3); the heat treatment temperature is 600-900 ℃.
Further, in the third step, porous SiOx/Si/Li2SiOyThe mass ratio of the compound to the carbon matrix material is 1 (1-4); the solvent is one or more of alcohols, ketones, alkanes and lipids; the wet grinding time is 1h-12 h.
Further, in the fourth step, the high-temperature carbonization is carried out by two-stage temperature rise under inert atmosphere, the temperature is firstly preserved for 1h-4h at 200 ℃ to 450 ℃, then is raised to 750 ℃ to 950 ℃, and is preserved for 1h-6h, the inert atmosphere is non-oxidizing atmosphere, and the non-oxidizing atmosphere is at least one of nitrogen, argon and helium.
Further, in the fourth step, when the gas phase is coated at the temperature of 750-950 ℃, organic carbon source gas is introduced for reaction for 1-6 h; the organic carbon source gas is at least one of methane, acetylene and natural gas or is combined with hydrogen.
And further, crushing, screening and demagnetizing the silicon-based negative electrode material obtained in the fourth step.
Compared with the prior art, the invention has at least the following beneficial effects:
the silicon-based negative electrode material provided by the invention comprises a core, a porous middle layer and a shell, wherein the core is a carbon matrix material, and the middle layer is porous SiOx/Si/Li2SiOy compound, Si-SiOx can raise specific energy and first effect of material, Li can raise material circulation stability, SiOx/Si/Li2The porous structure of the SiOy compound reserves an expansion space for the silicon material; the outer shell is carbonThe coating layer improves the machining performance and the conductivity of the silicon-based negative electrode material, and the finally obtained silicon-based negative electrode material is stable in property, not easy to expand and good in machining performance and conductivity.
The silicon-based negative electrode material provided by the invention takes the diatomite as a raw material, and the porous structure of the diatomite is utilized to realize the reservation of the expansion space, so that the expansion problem of the silicon-based negative electrode is effectively improved; obtaining porous SiO after the diatomite pretreatment2In the thermal reduction process, metal lithium is used as a reducing agent, the reaction degree is reasonably controlled, and SiOx preparation and material pre-lithium are realized while other impurities are not introduced; according to the invention, the diatomite is used as a silicon source, so that the use of nano silicon materials is avoided, and the cost of raw materials is reduced.
According to the silicon-based negative electrode material, high-temperature carbonization is carried out before the surface of the silicon-based negative electrode material is coated with the carbon coating layer, some organic matters or additives in the previous steps are carbonized through the high-temperature carbonization, so that the state of the previous steps is only physically wrapped is more stable, and the carbon coating layer is further coated outside the middle porous layer through gas phase wrapping, so that the mechanical processing performance and the electrical conductivity of the silicon-based negative electrode material and the cycling stability of the silicon-based negative electrode material in the charging and discharging process are improved.
Drawings
Fig. 1 is a schematic structural diagram of a silicon-based negative electrode material in the invention.
In the drawings: 1 is an inner core; 2 is an intermediate porous layer; 3 is a shell
Detailed Description
The invention is further described with reference to the following figures and detailed description.
Example 1
(1) Pretreating diatomite: keeping the temperature of the diatomite at 400 ℃ for 4 hours, and removing organic matters; then crushing, acid washing and water washing are carried out on the diatomite after the heat treatment, wherein the acid washing adopts sulfuric acid with the mass fraction being more than 70%, the acid washing is carried out for 2 hours at the temperature of 70 ℃ and the liquid-solid ratio of 5:1, and the acid washing and the water washing are alternately carried out until the pH value of the washing liquid is between 6 and 8; then drying and crushing the diatomite subjected to acid washing and water washing to finally obtain the purified porous SiO2And (3) powder.
(2)SiOx/Si/Li2SiOy compound preparation: lithium powder and porous SiO with the mass ratio of 1:0.52Uniformly mixing the powders, and performing heat treatment at 750 ℃ in a nitrogen atmosphere to obtain porous SiOx/Si/Li2SiOy composite, SiOx/Si/Li obtained by incomplete reaction of lithium powder and porous SiO2 powder2In the SiOy compound, x is more than or equal to 1 and less than or equal to 2, and y is more than or equal to 3 and less than or equal to 5.
(3) Preparing precursor slurry: respectively adding the porous SiOx/Si/Li2SiOy compound, crystalline flake graphite and a dispersing agent into ethanol, and grinding for 6h by a wet method to obtain uniformly dispersed precursor slurry, wherein the porous SiOx/Si/Li is2The mass ratio of the SiOy compound to the crystalline flake graphite is 1: 4.
(4) Preparing a negative electrode material: carrying out spray drying, fusion and granulation on the obtained precursor slurry, then carrying out high-temperature carbonization, and then carrying out gas phase coating to finally obtain the silicon-based anode material, wherein the reaction condition of the high-temperature carbonization is that the temperature is kept for 1h at 450 ℃, then the temperature is raised to 750 ℃, and the temperature is kept for 6 h; and the gas phase coating condition is that methane is introduced at 750 ℃, the reaction is carried out for 6 hours, the silicon-based anode material is obtained, and the silicon-based anode material is crushed, screened and demagnetized.
Example 2
(1) Pretreating diatomite: keeping the temperature of the diatomite at 750 ℃ for 1h, and removing organic matters; then crushing, acid washing and water washing, wherein the acid washing adopts sulfuric acid with the mass fraction of more than 70%, the acid washing is carried out for 1h at the temperature of 100 ℃ and the liquid-solid ratio of 2:1, and the acid washing and the water washing are alternately carried out until the pH value of the washing liquid is between 6 and 8; drying and crushing the diatomite subjected to acid washing and water washing to obtain purified porous SiO2And (3) powder.
(2)SiOx/Si/Li2SiOy compound preparation: lithium powder and porous SiO with the mass ratio of 1:32Uniformly mixing the powders, and performing heat treatment at 600 ℃ in an argon atmosphere to obtain porous SiOx/Si/Li2SiOy complexes.
(3) Preparing precursor slurry: porous SiOx/Si/Li2Adding SiOy compound, crystalline flake graphite, soft carbon compound and dispersant into ethanol and acetone respectively, and wet grinding for 12h to obtain uniformly dispersed precursor slurry, wherein porous SiOx/Si/Li2The mass ratio of the SiOy compound to the compound of the flake graphite and the soft carbon is 1: 1.
(4) Preparing a negative electrode material: carrying out spray drying, fusion and granulation on the obtained precursor slurry, then carrying out high-temperature carbonization, and then carrying out gas phase coating to finally obtain the silicon-based anode material, wherein the reaction condition of the high-temperature carbonization is that the temperature is kept for 4 hours at 200 ℃, then the temperature is raised to 950 ℃, and the temperature is kept for 1 hour; the reaction condition of gas phase coating is that mixed gas of acetylene and natural gas is introduced at 950 ℃, reaction is carried out for 1h, the silicon-based anode material is obtained, and crushing, screening and demagnetizing are carried out on the silicon-based anode material.
Example 3
(1) Pretreating diatomite: carrying out heat treatment on the diatomite at 600 ℃, preserving heat for 2 hours, and removing organic matters in the diatomite; then crushing, acid washing and water washing are carried out on the diatomite without organic matters, wherein the acid washing adopts sulfuric acid with the mass fraction being more than 70%, the acid washing is carried out for 4 hours at the temperature of 85 ℃ and the liquid-solid ratio being 3:1, and the acid washing and the water washing are alternately carried out until the pH value of the washing liquid is between 6 and 8; then drying and crushing the diatomite subjected to acid washing and water washing to obtain purified porous SiO2And (3) powder.
(2)SiOx/Si/Li2SiOy compound preparation: lithium powder and porous SiO with the mass ratio of 1:12Uniformly mixing the powders, and performing heat treatment at 900 ℃ in helium atmosphere to obtain porous SiOx/Si/Li2SiOy complexes.
(3) Preparing precursor slurry: porous SiOx/Si/Li2And respectively adding the SiOy compound, the compound of hard carbon and artificial graphite and a dispersing agent into ethanol, and carrying out wet grinding for 1h to obtain uniformly dispersed precursor slurry, wherein the mass ratio of the porous SiOx/Si/Li2SiOy compound to the hard carbon is 1: 2.
(4) Preparing a negative electrode material: carrying out spray drying, fusion and granulation on the obtained precursor slurry, then carrying out high-temperature carbonization, then carrying out gas phase coating to obtain a silicon-based anode material, and crushing, screening and demagnetizing the obtained silicon-based anode material, wherein the reaction condition of high-temperature carbonization is that the temperature is kept at 350 ℃ for 2h, then the temperature is raised to 850 ℃ and the temperature is kept for 2 h; the reaction condition of the gas phase coating is that mixed gas of natural gas and hydrogen is introduced at the temperature of 800 ℃, the reaction is carried out for 1h, the silicon-based anode material is obtained, and the silicon-based anode material is crushed, screened and demagnetized.
The silicon-based negative electrode material obtained in the above examples 1 to 3 is used as a negative electrode to be subjected to slurry preparation, coating and drying to obtain a negative electrode plate, and a metal lithium plate is used as a counter electrode to assemble a battery and perform electrochemical test, wherein the specific test method comprises the following steps: 1mol/L LiPF6/EC + DMC + EMC (V/V1: 1:1) electrolyte and Celgard2400 diaphragm are assembled into a 2025 button cell. Adopting a LanD battery test system of Wuhanjinnuo electronic Limited to carry out normal temperature test, wherein the test conditions are as follows: the first charge and discharge I is 0.1C, the cycle I is 0.1C, the voltage range is 0.005-2.0V, and the test results are shown in Table 1.
TABLE 1 test results of electrochemical properties of negative electrode materials
Technical index First reversible capacity/mAh.g-1 First effect/%) 100thCapacity retention ratio/%)
Example 1 1102 93.2 95.8
Example 2 1988 91.0 93.3
Example 3 1573 92.7 95.3
The test results in table 1 show that the silicon-based negative electrode materials obtained under different Si/C ratios can maintain higher first coulombic efficiency, and the capacity retention rate is more than 93% after 100 cycles of 1C charge-discharge cycle, which indicates that the negative electrode material effectively inhibits the problem of particle breakage caused by Si expansion, and the obtained silicon-based negative electrode material has stable structure and better electrochemical performance.
FIG. 1 is a schematic structural diagram of a silicon-based negative electrode material of the present invention, in which an inner core is a carbon matrix material, and a porous intermediate layer of a porous intermediate layer is porous SiO prepared by using diatomite as a silicon sourcex/Si/Li2OyThe shell of the composite is a carbon coating layer, and the silicon-based negative electrode material has a stable structure, is not easy to expand and has better machining performance and electrical conductivity.

Claims (10)

1. The silicon-based negative electrode material is characterized by comprising an inner core (1), an outer shell (3) and a porous middle layer (2) between the inner shell (1) and the outer shell, wherein the porous middle layer (2) is SiOx/Si/Li2SiOyAnd (c) a complex.
2. The silicon-based anode material according to claim 1, wherein the core (1) is a carbon matrix material, the porous intermediate layer (2) is a silicon source of diatomite, and the outer shell (3) is a carbon coating layer, wherein the carbon matrix material is at least one of natural graphite, artificial graphite, soft carbon and hard carbon, and the natural graphite is flake graphite.
3. The preparation method of the silicon-based negative electrode material is characterized by comprising the following steps of:
step one, diatomite is pretreated to obtain purified porous SiO2Powder;
step two, the porous SiO obtained in the step one2Mixing the powder with lithium powder, and carrying out heat treatment under protective atmosphere to obtain porous SiOx/Si/Li2SiOyA complex;
step three, mixing the carbon matrix material, the dispersing agent and the porous SiO obtained in the step twox/Si/Li2SiOyDispersing the compound in a solvent, and grinding to obtain precursor slurry;
and step four, carrying out spray drying, fusion and granulation on the precursor slurry obtained in the step three, and then carrying out high-temperature carbonization and gas phase coating to obtain the silicon-based negative electrode material.
4. The method for preparing the silicon-based anode material as claimed in claim 3, wherein the diatomite pretreatment in the first step is specifically operated as follows: heat treating diatomite to eliminate organic matter, crushing, acid washing, water washing, stoving and crushing to obtain purified porous SiO2Powder; the heating temperature of the heat treatment is 400-750 ℃, and the heat preservation is carried out for 1-4 h; the acid washing is carried out for 1h-4h at 70-100 ℃ by adopting sulfuric acid with the mass fraction of more than 70 percent and the liquid-solid ratio of (2-5) to 1; the acid wash and water wash are alternated until the pH of the wash is between 6 and 8.
5. The method for preparing the silicon-based anode material as claimed in claim 3, wherein in the second step, the lithium powder and SiO are added2Mixing the powder according to the mass ratio of 1 (0.5-3), and mixing the mixed lithium powder and SiO2The heat treatment temperature of the powder is 600-900 ℃.
6. The method for preparing the silicon-based anode material as claimed in claim 3, wherein in the third step, the porous SiO isx/Si/Li2SiOyThe composite and the carbon matrix material are dispersed in a solvent according to the mass ratio of 1 (1-4) and are subjected to wet grinding, wherein the solvent is one or more of alcohols, ketones, alkanes and lipids, and the wet grinding time is 1h-12 h.
7. The method for preparing the silicon-based anode material according to claim 3, wherein in the fourth step, the high-temperature carbonization is carried out by two-stage temperature rise under an inert atmosphere, the temperature is firstly kept at 200-450 ℃ for 1-4 h, then is kept at 750-950 ℃ for 1-6 h, and the inert atmosphere is a non-oxidizing atmosphere.
8. The method for preparing the silicon-based anode material as claimed in claim 7, wherein the non-oxidizing atmosphere is at least one of nitrogen, argon and helium.
9. The method for preparing the silicon-based anode material according to claim 3, wherein in the fourth step, organic carbon source gas is introduced when the gas phase is coated at the temperature of 750-950 ℃ for reaction for 1-6 h; the organic carbon source gas is at least one of methane, acetylene and natural gas or is combined with hydrogen.
10. The method for preparing the silicon-based anode material according to claim 3, wherein the silicon-based anode material obtained in the fourth step is crushed, sieved and demagnetized.
CN202010997891.8A 2020-09-21 2020-09-21 Silicon-based negative electrode material and preparation method thereof Active CN112133898B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010997891.8A CN112133898B (en) 2020-09-21 2020-09-21 Silicon-based negative electrode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010997891.8A CN112133898B (en) 2020-09-21 2020-09-21 Silicon-based negative electrode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112133898A true CN112133898A (en) 2020-12-25
CN112133898B CN112133898B (en) 2022-04-19

Family

ID=73841948

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010997891.8A Active CN112133898B (en) 2020-09-21 2020-09-21 Silicon-based negative electrode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112133898B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113659115A (en) * 2021-08-20 2021-11-16 山东省泥博士新型材料有限公司 Process for preparing silicon lithium battery cathode with multilevel structure by using diatomite

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101710617A (en) * 2009-05-12 2010-05-19 大连丽昌新材料有限公司 High-energy silicon-carbon composite negative electrode material for lithium ion battery and manufacturing process thereof
CN102208636A (en) * 2011-05-12 2011-10-05 北京科技大学 Method for preparing porous silicon/carbon composite material by using diatomite as raw material and application
CN102903896A (en) * 2012-10-22 2013-01-30 深圳清华大学研究院 Silicon carbon composite negative electrode material for lithium ion battery as well as preparation method and applications of material
CN103022446A (en) * 2012-12-19 2013-04-03 深圳市贝特瑞新能源材料股份有限公司 Silicon oxide/carbon cathode material of lithium ion battery and preparation method of material
CN103337613A (en) * 2013-07-04 2013-10-02 奇瑞汽车股份有限公司 Silicon-carbon composite material and preparation method thereof, and lithium ion battery
CN103633306A (en) * 2012-08-28 2014-03-12 华为技术有限公司 Silicon-carbon composite negative electrode material and preparation method thereof, and lithium ion battery
CN103730644A (en) * 2013-12-12 2014-04-16 天津巴莫科技股份有限公司 Preparation method of silicon-silicon oxide-carbon composite negative pole material of lithium ion battery
US20150162617A1 (en) * 2013-12-09 2015-06-11 Nano And Advanced Materials Institute Limited Si@C core/shell Nanomaterials for High Performance Anode of Lithium Ion Batteries
CN105680026A (en) * 2016-04-21 2016-06-15 苏州协鑫集成科技工业应用研究院有限公司 Carbon composite material, preparation method for carbon composite material and battery
CN108269979A (en) * 2017-12-28 2018-07-10 合肥国轩高科动力能源有限公司 A kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation and preparation method thereof
JP2018152161A (en) * 2017-03-09 2018-09-27 株式会社豊田自動織機 Negative electrode material
CN108807862A (en) * 2017-05-03 2018-11-13 溧阳天目先导电池材料科技有限公司 A kind of silicon based composite material and preparation method thereof, negative material and lithium battery
CN109768246A (en) * 2018-12-29 2019-05-17 湖南中科星城石墨有限公司 A kind of nano-silicon composite anode materials and preparation method thereof for lithium ion battery
CN109786704A (en) * 2019-01-15 2019-05-21 江汉大学 A kind of preparation of silicon carbon composite materials method based on the mineral containing silica
CN110224125A (en) * 2019-06-13 2019-09-10 长沙矿冶研究院有限责任公司 A kind of porous carbon-nanometer silico-carbo Core-shell structure material and preparation method thereof
CN110911643A (en) * 2019-12-05 2020-03-24 江苏科技大学 Diatomite-based lithium ion battery negative electrode material and preparation method thereof
CN111362269A (en) * 2020-03-09 2020-07-03 上海电气集团股份有限公司 Preparation method of SEI (solid electrolyte interphase) film of lithium ion battery cathode, lithium ion battery cathode material and application of lithium ion battery cathode material

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101710617A (en) * 2009-05-12 2010-05-19 大连丽昌新材料有限公司 High-energy silicon-carbon composite negative electrode material for lithium ion battery and manufacturing process thereof
CN102208636A (en) * 2011-05-12 2011-10-05 北京科技大学 Method for preparing porous silicon/carbon composite material by using diatomite as raw material and application
CN103633306A (en) * 2012-08-28 2014-03-12 华为技术有限公司 Silicon-carbon composite negative electrode material and preparation method thereof, and lithium ion battery
CN102903896A (en) * 2012-10-22 2013-01-30 深圳清华大学研究院 Silicon carbon composite negative electrode material for lithium ion battery as well as preparation method and applications of material
CN103022446A (en) * 2012-12-19 2013-04-03 深圳市贝特瑞新能源材料股份有限公司 Silicon oxide/carbon cathode material of lithium ion battery and preparation method of material
CN103337613A (en) * 2013-07-04 2013-10-02 奇瑞汽车股份有限公司 Silicon-carbon composite material and preparation method thereof, and lithium ion battery
US20150162617A1 (en) * 2013-12-09 2015-06-11 Nano And Advanced Materials Institute Limited Si@C core/shell Nanomaterials for High Performance Anode of Lithium Ion Batteries
CN103730644A (en) * 2013-12-12 2014-04-16 天津巴莫科技股份有限公司 Preparation method of silicon-silicon oxide-carbon composite negative pole material of lithium ion battery
CN105680026A (en) * 2016-04-21 2016-06-15 苏州协鑫集成科技工业应用研究院有限公司 Carbon composite material, preparation method for carbon composite material and battery
JP2018152161A (en) * 2017-03-09 2018-09-27 株式会社豊田自動織機 Negative electrode material
CN108807862A (en) * 2017-05-03 2018-11-13 溧阳天目先导电池材料科技有限公司 A kind of silicon based composite material and preparation method thereof, negative material and lithium battery
CN108269979A (en) * 2017-12-28 2018-07-10 合肥国轩高科动力能源有限公司 A kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation and preparation method thereof
CN109768246A (en) * 2018-12-29 2019-05-17 湖南中科星城石墨有限公司 A kind of nano-silicon composite anode materials and preparation method thereof for lithium ion battery
CN109786704A (en) * 2019-01-15 2019-05-21 江汉大学 A kind of preparation of silicon carbon composite materials method based on the mineral containing silica
CN110224125A (en) * 2019-06-13 2019-09-10 长沙矿冶研究院有限责任公司 A kind of porous carbon-nanometer silico-carbo Core-shell structure material and preparation method thereof
CN110911643A (en) * 2019-12-05 2020-03-24 江苏科技大学 Diatomite-based lithium ion battery negative electrode material and preparation method thereof
CN111362269A (en) * 2020-03-09 2020-07-03 上海电气集团股份有限公司 Preparation method of SEI (solid electrolyte interphase) film of lithium ion battery cathode, lithium ion battery cathode material and application of lithium ion battery cathode material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
XIE, LZ 等: "Modified SiO hierarchical structure materials with improved initial coulombic efficiency for advanced lithium-ion battery anodes", 《RSC ADVANCES》 *
於洪将: "硅/碳和Li4Ti5O12负极材料的研究", 《中国优秀硕士学位论文全文数据库》 *
沈晓辉 等: "锂离子电池硅碳负极材料研究进展", 《硅酸盐学报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113659115A (en) * 2021-08-20 2021-11-16 山东省泥博士新型材料有限公司 Process for preparing silicon lithium battery cathode with multilevel structure by using diatomite

Also Published As

Publication number Publication date
CN112133898B (en) 2022-04-19

Similar Documents

Publication Publication Date Title
CN108598390B (en) Preparation method of positive electrode material for lithium-sulfur battery and lithium-sulfur battery
CN107275606B (en) Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof
CN112125294B (en) Coal-based silicon-carbon composite negative electrode material and preparation method thereof
CN112421048A (en) Method for preparing graphite-coated nano-silicon lithium battery negative electrode material at low cost
CN105428618B (en) A kind of preparation method and applications of core-shell type carbon-clad metal sulfide nano-complex particle
CN110518213A (en) A kind of porous silicon-carbon nano tube compound material and its preparation method and application
CN112687867B (en) Composite negative electrode material, preparation method thereof and lithium ion battery
CN102593415A (en) Preparation method for positive electrode of lithium ion battery
CN112652758B (en) Silicon oxide/carbon microsphere composite negative electrode material for lithium ion battery and preparation method thereof
CN111769272A (en) Bi @ C hollow nanosphere composite material and preparation method and application thereof
CN111009647A (en) Lithium borosilicate alloy cathode active material of lithium secondary battery, cathode, preparation and application thereof
CN107919477A (en) A kind of application of mixed expanded graphite as lithium ion battery negative material
CN111653734A (en) Ferrosilicon/carbon composite lithium ion battery cathode material and preparation method and application thereof
CN114291796A (en) Potassium ion battery negative electrode material and preparation method and application thereof
CN114388738B (en) Silicon-based anode material and preparation method and application thereof
CN110649234A (en) Preparation method of silicon-based negative electrode material with high coulombic efficiency
CN112133898B (en) Silicon-based negative electrode material and preparation method thereof
CN114520328B (en) Lithium ion battery negative electrode material, preparation method thereof, negative electrode and battery
CN110600710B (en) Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery
CN112142060B (en) Coal-based silicon-carbon composite negative electrode material and preparation method thereof
CN107910540B (en) Preparation method of carbon-silicon negative electrode material and lithium ion battery
CN110797517A (en) Preparation method of nickel-silver alloy particle doped silicon-carbon negative electrode material
CN111348685B (en) Graphene-based composite material and preparation method and application thereof
CN114079044B (en) Three-dimensional porous silicon/graphene composite anode material, preparation method thereof and lithium ion battery
CN109879286B (en) Preparation method of lithium battery silicon-carbon negative electrode composite material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant