CN112271289A - High-first-efficiency pre-lithiated silicon monoxide negative electrode material and preparation method and application thereof - Google Patents

High-first-efficiency pre-lithiated silicon monoxide negative electrode material and preparation method and application thereof Download PDF

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CN112271289A
CN112271289A CN202011197191.7A CN202011197191A CN112271289A CN 112271289 A CN112271289 A CN 112271289A CN 202011197191 A CN202011197191 A CN 202011197191A CN 112271289 A CN112271289 A CN 112271289A
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negative electrode
silicon monoxide
efficiency
electrode material
lithiated
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薛孟尧
宋骞
胥鑫
王凯锋
霍林智
曹新龙
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Shaanxi Coal and Chemical Technology Institute 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
    • H01M4/48—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
    • 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
    • H01M4/62—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
    • 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 high-first-efficiency pre-lithiated silicon monoxide negative electrode material as well as a preparation method and application thereof, and belongs to the field of negative electrode active material materials of lithium ion batteries. According to the invention, the silicon monoxide/carbon composite material powder is pressed into tablets, the tablets and the metal lithium form a counter electrode, the obtained counter electrode is subjected to constant current discharge under an external circuit until the counter electrode reaches a cut-off voltage, so that a pre-lithiated silicon monoxide/carbon composite sheet with active lithium removed is obtained, and the obtained pre-lithiated silicon monoxide/carbon composite sheet is subjected to thermal sintering, so that the high-efficiency pre-lithiated silicon monoxide negative electrode material is obtained. The high-first-efficiency silicon monoxide is prepared by vapor deposition, electrochemical lithium pre-supplement and heat treatment, and the high-first-efficiency silicon monoxide contains crystalline silicate and most of Li2SiO3The first of the obtained high-first-efficiency pre-lithiated silicon monoxide cathode materialThe sub-coulombic efficiency can reach 84.2% -93.4%, so that the method can be used for preparing the lithium ion battery.

Description

High-first-efficiency pre-lithiated silicon monoxide negative electrode material and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium ion battery negative active material, and relates to a high-first-efficiency pre-lithiated silicon monoxide negative electrode material, and a preparation method and application thereof.
Background
The silicon-based material is considered as the next generation ideal lithium ion battery negative electrode, and 4100mA · h · g thereof-1The mass specific capacity of the graphite anode is ten times that of the graphite anode commercialized at present, and the graphite anode has the advantages of a lower voltage platform, a cheap acquisition mode and the like, but the practical application of the graphite anode is limited by the defects that the volume expansion of the graphite anode in the charging and discharging process can cause material inactivation, and the low conductivity and the like.
For the defects of the silicon-based negative electrode material, the carbon coating can effectively improve, for example, in the patent, graphene is used for inhibiting the volume expansion of the silicon oxide negative electrode and improving the conductivity, and the method is an effective method. In the current commercialized silicon carbon negative electrode, 3% -5% of the silicon monoxide negative electrode is added to effectively improve the energy density of the battery, but the first coulombic efficiency of the current conventional silicon monoxide negative electrode is only 76% -77%, so that higher doping amount is limited.
The method for improving the first effect of the silicon monoxide at present is to pre-supplement lithium ions to pre-consume irreversible components of the silicon monoxide, so that the first coulombic efficiency of the silicon monoxide can be improved to 85% -90%. The existing lithium pre-supplementing method mainly comprises solid-phase thermal doping, redox pre-lithium and electrochemical pre-lithium, wherein the solid-phase thermal doping and the redox pre-lithium are reported more, the first effect of the silicon oxide can be improved to about 90 percent and still lower than that of graphite by 93 to 94 percent, and the first effect of the silicon oxide can be improved to 93 percent or even higher by utilizing the electrochemical pre-lithium.
At present, electrochemical lithium pre-charging is researched more on a pole piece, while electrochemical lithium charging is researched less on a material end, and the difficulties lie in that the resistivity of silicon oxide is high, the electrochemical dynamic performance is poor, and lithium ions are difficult to be inserted. On one hand, the carbon coating is adopted, the excellent conductivity of pyrolytic carbon is utilized to improve the intercalation rate of lithium ions, on the other hand, the tabletting is adopted to ensure that the silicon oxide/carbon particles are tightly contacted, the intercalation rate of the lithium ions can also be improved, and the carbon coating and the lithium sheet are easy to form a counter electrode. However, the performance of the thin sheet pressed from the material is different from that of a battery pole piece, and because the thin sheet is lack of components such as a conductive agent, the polarization phenomenon is easy to occur on the upper surface of the thin sheet, especially when the thin sheet is thick, the polarization phenomenon is more obvious, and the thin sheet can only be embedded with a trace amount of lithium, so that the effect of lithium pre-supplement cannot be achieved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a high-first-efficiency pre-lithiated silicon monoxide negative electrode material, and a preparation method and application thereof. The invention solves the problem of low first coulombic efficiency of the silicon monoxide material.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention relates to a preparation method of a high-first-efficiency pre-lithiated silicon oxide negative electrode material.
Preferably, the preparation method of the high-first-efficiency pre-lithiated silicon monoxide negative electrode material specifically comprises the following steps:
s1, introducing a pyrolysis gas source to carry out carbon coating treatment on the surface of the silicon oxide by a vapor deposition method, and then crushing to obtain silicon oxide/carbon composite powder;
s2, tabletting the obtained silicon monoxide/carbon composite powder, forming a counter electrode with metal lithium, performing constant-current discharge under an external circuit until the counter electrode reaches a cut-off voltage, removing active lithium, and cleaning to obtain a pre-lithiated silicon monoxide/carbon composite sheet;
and S3, carrying out thermal sintering on the pre-lithiated silicon oxide/carbon composite sheet in an inert atmosphere to obtain the high-first-efficiency pre-lithiated silicon oxide negative electrode material.
Further preferably, in the step S1, the pyrolysis temperature is 700-1000 ℃, and the heat preservation time is 3-5 h; the pyrolysis gas source is one or more of acetylene, methane, ethylene and propylene.
Further preferably, in step S2, the thickness of the tablet is 50 to 200 μm.
More preferably, in step S2, the constant current discharge current is 0.01 to 20mA · h · g-1The cut-off voltage is 0.2-0.4V.
Further preferably, in step S2, the operation of removing active lithium includes: lithium ions are extracted by charging, or active lithium is inactivated by washing with acidic water, pure water, alkaline water, or alcohol.
Further preferably, in step S3, the temperature of the thermal sintering is 500-700 ℃, and the heat preservation time is 3-5 hours.
The invention discloses a high-first-efficiency pre-lithiated silicon monoxide negative electrode material prepared by the preparation method.
Preferably, the high-first-efficiency pre-lithiated silicon monoxide negative electrode material internally contains crystalline Si and Li2SiO3And Li2Si2O5At least one of (1); the first coulombic efficiency can reach 80.6-93.4%.
The invention also discloses application of the high-first-efficiency pre-lithiated silicon monoxide negative electrode material in preparation of a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a high-first-efficiency pre-lithiated silicon oxide negative electrode material, which comprises the steps of firstly carrying out pyrolytic carbon coating on silicon oxide to improve the conductivity of the silicon oxide, facilitating the intercalation of lithium ions, then pressing silicon oxide/carbon composite material powder into a sheet shape, forming a counter electrode with metal lithium, embedding lithium under a small current to consume a part of irreversible components in advance, then cleaning the material with dimethyl carbonate, and then inactivating active lithium, on the other hand, adjusting silicate components in the pre-lithiated silicon oxide through heat treatment, and improving the water resistance of the silicon oxide/carbon composite material. According to the invention, lithium is supplemented to the silicon oxide/carbon composite material by an electrochemical lithium pre-preparation method, so that the first effect is improved, and the problem of low first coulombic efficiency of the silicon oxide material is solved.
The invention also discloses the high-first-effect pre-lithiated silicon monoxide cathode material prepared by the preparation method, the first effect of the obtained high-first-effect pre-lithiated silicon monoxide cathode material can be improved to 84.2% -93.4% by adopting the electrochemical pre-lithiation, the high-first-effect pre-lithiated silicon monoxide cathode material is close to the current commercial graphite cathode, and the high-first-effect pre-lithiated silicon monoxide cathode material is higher than the pre-lithiated silicon monoxide cathode materials prepared by other methods such as solid-phase pre-lithiation and liquid-phase pre-lithiation, and the high-first-effect pre-lithiated silicon monoxide.
The invention also discloses application of the high-first-efficiency pre-lithiated silicon monoxide negative electrode material in preparation of a lithium ion battery, and the silicon monoxide negative electrode material is convenient for large-scale application of a silicon monoxide material in the field of lithium ion battery materials.
Drawings
FIG. 1 is a graph showing the result of XRD test of a negative electrode material for a silicon oxide battery prepared in example 1 of the present invention;
FIG. 2 is a graph showing the result of XRD test of the negative electrode material of a silicon oxide cell prepared in example 4 of the present invention;
fig. 3 is a graph showing XRD test results of the negative electrode material of a silicon oxide battery prepared in example 5 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
A preparation method of a high-first-efficiency pre-lithiated silicon monoxide negative electrode material comprises the following steps:
s1, placing the silicon monoxide in a rotary kiln, heating to a certain temperature, introducing pyrolysis gas, preserving heat for a period of time to obtain a silicon monoxide/carbon composite material, and crushing to a proper particle size to obtain silicon monoxide/carbon composite material powder;
s2, pressing the silicon monoxide/carbon composite material powder into a sheet shape, forming a counter electrode with metal lithium, performing constant current discharge under an external circuit until the counter electrode is cut off, removing active lithium, cleaning the material with dimethyl carbonate, removing surface electrolyte and drying to obtain a pre-lithiated silicon monoxide/carbon composite sheet without the active lithium;
and S3, carrying out inert atmosphere thermal sintering on the pre-lithiated silicon oxide/carbon composite sheet to obtain the final high-efficiency pre-lithiated silicon oxide negative electrode material.
In the step S1, the pyrolysis temperature is 700-1000 ℃, the pyrolysis gas source is one or a mixture of two or more of acetylene, methane, ethylene, propylene and the like, the heat preservation time is 3-5 h, the carbon coating amount is 1% -20%, and the carbon coating thickness is 50-5000 nm.
In step S1, the median particle diameter of the pulverized silica/carbon composite material powder is 4-6 microns.
In step S2, the equipment used for tabletting is grinding, isostatic pressing, etc.
In the step S2, the pressure used for tabletting is 20-40 Mpa, and the thickness of the tabletting is 50-200 microns.
Wherein, in the step S2, in the battery with the counter electrode formed by the lithium metal, the constant current discharge current of the external circuit is 0.01-20 mA.h.g-1The cut-off voltage is 0.2V-0.4V.
In the step S2, the step of removing active lithium may be performed by removing lithium ions by charging, or may be performed by deactivating active lithium by washing with acidic water, pure water, alkaline water, or alcohol.
In the step S3, the temperature of the thermal sintering is 500-700 ℃, the atmosphere is argon or nitrogen, and the heat preservation time is 3-5 h.
The present invention is further illustrated by the following specific examples.
Example 1
1) And (3) placing the silicon monoxide in a rotary kiln, heating to 800 ℃, introducing acetylene gas, and keeping the temperature for 5 hours to obtain the silicon monoxide/carbon composite material.
2) Pressing the silicon oxide/carbon composite material into sheets with the thickness of 100 microns by grinding and pressing, then assembling the sheets and metallic lithium into a battery, and controlling the power supply to be at 5 mA.h.g-1Discharging to 0.25V, removing active lithium, and cleaning the material with dimethyl carbonate to remove the electrolyte on the surface.
3) Sintering the obtained material for 3h at 650 ℃ in an argon atmosphere to obtain the final high-efficiency pre-lithiated silicon monoxide negative electrode material. Example 2
1) And (3) placing the silicon monoxide in a rotary kiln, heating to 800 ℃, introducing acetylene gas, and keeping the temperature for 5 hours to obtain the silicon monoxide/carbon composite material.
2) Pressing the silicon oxide/carbon composite material into sheets with the thickness of 100 microns by grinding and pressing, then assembling the sheets and metallic lithium into a battery, and controlling the power supply to be at 5 mA.h.g-1Discharging to 0.4V, removing active lithium, and cleaning the material with dimethyl carbonate to remove the electrolyte on the surface.
3) Sintering the obtained material for 3h at 650 ℃ in an argon atmosphere to obtain the final high-efficiency pre-lithiated silicon monoxide negative electrode material.
Example 3
1) And (3) placing the silicon monoxide in a rotary kiln, heating to 800 ℃, introducing acetylene gas, and keeping the temperature for 5 hours to obtain the silicon monoxide/carbon composite material.
2) Pressing the silicon oxide/carbon composite material into sheets with the thickness of 100 microns by grinding and pressing, then assembling the sheets and metallic lithium into a battery, and controlling the power supply to be at 5 mA.h.g-1Discharging to 0.2V, removing active lithium, and cleaning the material with dimethyl carbonate to remove the electrolyte on the surface.
3) Sintering the obtained material for 3h at 650 ℃ in an argon atmosphere to obtain the final high-efficiency pre-lithiated silicon monoxide negative electrode material.
Example 4
1) And (3) placing the silicon monoxide in a rotary kiln, heating to 800 ℃, introducing acetylene gas, and keeping the temperature for 5 hours to obtain the silicon monoxide/carbon composite material.
2) Pressing the silicon oxide/carbon composite material into sheets with the thickness of 100 microns by grinding and pressing, then assembling the sheets and metallic lithium into a battery, and controlling the power supply to be at 5 mA.h.g-1Discharging to 0.4V, removing active lithium, and cleaning the material with dimethyl carbonate to remove the electrolyte on the surface.
3) Sintering the obtained material for 3h at 500 ℃ in an argon atmosphere to obtain the final high-efficiency pre-lithiated silicon monoxide negative electrode material.
Example 5
1) And (3) placing the silicon monoxide in a rotary kiln, heating to 800 ℃, introducing acetylene gas, and keeping the temperature for 5 hours to obtain the silicon monoxide/carbon composite material.
2) Pressing the silicon oxide/carbon composite material into sheets with the thickness of 100 microns by grinding and pressing, then assembling the sheets and metallic lithium into a battery, and controlling the power supply to be at 5 mA.h.g-1Discharging to 0.4V, removing active lithium, and cleaning the material with dimethyl carbonate to remove the electrolyte on the surface.
3) Sintering the obtained material for 3h at 700 ℃ in an argon atmosphere to obtain the final high-efficiency pre-lithiated silicon monoxide negative electrode material.
The electrochemical performance tests of the high-first-efficiency pre-lithiated silicon oxide negative electrode materials obtained in examples 1 to 5 are shown in table 1. Button cell test conditions: constant temperatureAt 25 ℃, LR2032, the first charge and discharge I is 0.1C, the cycle I is 0.1C, and the voltage range is 0.005-1.5V vs Li/Li+。
TABLE 1
Figure BDA0002754367670000071
From the experimental test results of the above examples 1 to 5, it can be seen that high-first-effect pre-lithiated silicon oxide negative electrode materials with different first effects are prepared by changing the lithium intercalation degree by changing the cut-off voltage, wherein the lower the cut-off voltage, the higher the first effect, but more lithium silicon alloy is generated, the post-treatment process has an influence on the performance of the sample, and the cycle performance in example 3 is somewhat reduced. In example 1, as compared with examples 4 and 5, it was found that the kind of silicate formed by changing the sintering temperature and the Li formed in the electrochemical pre-lithium process4SiO4Mainly amorphous, no change at low temperature, and amorphous Li with increasing temperature4SiO4First converted to Li2SiO3Is converted into Li again2SiO5。
Example 6
1) And (3) placing the silicon monoxide in a rotary kiln, heating to 900 ℃, introducing methane gas, and preserving heat for 3 hours to obtain the silicon monoxide/carbon composite material.
2) Pressing the silicon oxide/carbon composite material into sheets with the thickness of 50 microns by grinding and pressing, then assembling the sheets and metallic lithium into a battery, and controlling the power supply to be at 5 mA.h.g-1The current was discharged to 0.4V, and then activated lithium was removed by alcohol elution and the material was washed with dimethyl carbonate to remove electrolyte from the surface.
3) Sintering the obtained material for 3h at 600 ℃ in an argon atmosphere to obtain the final high-efficiency pre-lithiated silicon monoxide negative electrode material.
By adopting the experimental conditions, the first coulombic efficiency of the sample obtained in the embodiment can reach 93.4%.
Example 7
1, putting the silicon monoxide into a rotary kiln, heating to 850 ℃, introducing mixed gas of ethylene and methane, and preserving heat for 4 hours to obtain the silicon monoxide/carbon composite material.
2 pressing the silicon oxide/carbon composite material into a sheet with the thickness of 200 microns through grinding and pressing, then assembling the sheet and metal lithium into a battery, and controlling the power supply to be at the power of 20 mA.h.g-1Discharging to 0.2V, washing with water to remove active lithium, and washing with dimethyl carbonate to remove electrolyte on the surface.
3 sintering the obtained material for 3h at 700 ℃ in the argon atmosphere to obtain the final high-efficiency pre-lithiated silicon monoxide negative electrode material.
By adopting the experimental conditions, the first coulombic efficiency of the sample obtained in the embodiment can reach 90.9%.
Example 8
1) And (3) placing the silicon monoxide in a rotary kiln, heating to 700 ℃, introducing propylene gas, and preserving heat for 10 hours to obtain the silicon monoxide/carbon composite material.
2) Pressing the silicon oxide/carbon composite material into sheets with the thickness of 50 microns by grinding and pressing, assembling the sheets and metal lithium into a battery, and controlling the current at 0.01 mA.h.g under an external power supply-1Discharging to 0.2V, removing active lithium, and cleaning the material with dimethyl carbonate to remove the electrolyte on the surface.
3) Sintering the obtained material for 5h at 500 ℃ in the nitrogen atmosphere to obtain the final high-efficiency pre-lithiated silicon monoxide negative electrode material.
By adopting the experimental conditions, the first coulombic efficiency of the sample obtained in the embodiment can reach 88.4%.
Example 9
1) And (3) placing the silicon monoxide in a rotary kiln, heating to 1000 ℃, introducing acetylene and propylene gas, and keeping the temperature for 1h to obtain the silicon monoxide/carbon composite material.
2) The silica/carbon composite material was pressed into 200 μm thick sheets by isostatic pressing, and then assembled with lithium metal into batteries at 20mA · h · g under external power-1Discharging to 0.3V, removing active lithium, and cleaning the material with dimethyl carbonate to remove the electrolyte on the surface.
3) Sintering the obtained material for 5h at 500 ℃ in the nitrogen atmosphere to obtain the final high-efficiency pre-lithiated silicon monoxide negative electrode material.
By adopting the experimental conditions, the first coulombic efficiency of the sample obtained in the embodiment can reach 92.7%.
The invention is described in further detail below with reference to the accompanying drawings:
referring to FIG. 1, it can be seen that only Li was contained in the sample prepared in example 12SiO3。
Referring to fig. 2, it can be seen that the sample prepared in example 4 has no particularly distinct peak.
Referring to FIG. 3, it can be seen that Li is contained in the sample prepared in example 52Si2O5And Si peak.
Through the comparison of three samples, the patent can control the type of silicate and the size of silicon crystal grains through the post-treatment temperature.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (10)

1. A preparation method of a high-first-efficiency pre-lithiated silicon oxide negative electrode material is characterized by pressing silicon oxide/carbon composite material powder into a sheet, forming a counter electrode with metal lithium, performing constant-current discharge on the obtained counter electrode under an external circuit until the counter electrode reaches a cut-off voltage to obtain a pre-lithiated silicon oxide/carbon composite sheet with active lithium removed, and performing thermal sintering on the obtained pre-lithiated silicon oxide/carbon composite sheet to obtain the high-first-efficiency pre-lithiated silicon oxide negative electrode material.
2. The method for preparing the high-first-efficiency pre-lithiated silicon oxide negative electrode material according to claim 1, comprising the following steps:
s1, introducing a pyrolysis gas source to carry out carbon coating treatment on the surface of the silicon oxide by a vapor deposition method, and then crushing to obtain silicon oxide/carbon composite powder;
s2, tabletting the obtained silicon monoxide/carbon composite powder, forming a counter electrode with metal lithium, performing constant-current discharge under an external circuit until the counter electrode reaches a cut-off voltage, removing active lithium, and cleaning to obtain a pre-lithiated silicon monoxide/carbon composite sheet;
and S3, carrying out thermal sintering on the pre-lithiated silicon oxide/carbon composite sheet in an inert atmosphere to obtain the high-first-efficiency pre-lithiated silicon oxide negative electrode material.
3. The preparation method of the high-first-efficiency pre-lithiated silicon monoxide negative electrode material as claimed in claim 2, wherein in the step S1, the pyrolysis temperature is 700-1000 ℃, and the heat preservation time is 3-5 h; the pyrolysis gas source is one or more of acetylene, methane, ethylene and propylene.
4. The method for preparing a high-efficiency pre-lithiated silicon oxide negative electrode material of claim 2, wherein in step S2, the thickness of the pressed sheet is 50 to 200 μm.
5. The method for preparing the high-first-efficiency prelithium silicon oxide negative electrode material according to claim 2, wherein in step S2, the constant current discharge current is 0.01-20 mA-h-g-1The cut-off voltage is 0.2-0.4V.
6. The method of claim 2, wherein the step of removing active lithium in step S2 comprises: lithium ions are extracted by charging, or active lithium is inactivated by washing with acidic water, pure water, alkaline water, or alcohol.
7. The method for preparing the high-first-efficiency pre-lithiated silicon monoxide negative electrode material as claimed in claim 2, wherein in the step S3, the temperature of the thermal sintering is 500-700 ℃, and the holding time is 3-5 h.
8. The high-first-efficiency pre-lithiated silicon monoxide negative electrode material prepared by the preparation method of any one of claims 1 to 7.
9. The high-first-efficiency pre-lithiated silicon monoxide negative electrode material of claim 8, wherein the high-first-efficiency pre-lithiated silicon monoxide negative electrode material contains crystalline Si and Li inside2SiO3And Li2Si2O5At least one of (1); the first coulombic efficiency can reach 80.6-93.4%.
10. Use of the high first-effect pre-lithiated silica negative electrode material of claim 8 for the preparation of a lithium ion battery.
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Application publication date: 20210126