CN114843496A - Silicon-based negative electrode material and preparation method and application thereof - Google Patents
Silicon-based negative electrode material and preparation method and application thereof Download PDFInfo
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- CN114843496A CN114843496A CN202210589494.6A CN202210589494A CN114843496A CN 114843496 A CN114843496 A CN 114843496A CN 202210589494 A CN202210589494 A CN 202210589494A CN 114843496 A CN114843496 A CN 114843496A
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- 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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
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- 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 belongs to the technical field of preparation of lithium battery materials, and particularly relates to a silicon-based negative electrode material and a preparation method and application thereof. The raw materials of the silicon-based negative electrode material comprise a non-metal silicon-containing material, a lithium source and ionic liquid; the melting point of the ionic liquid is lower than that of the lithium metal. The lithium in the silicon-based negative electrode material is Li 2 SiO 3 Phase, Li 2 Si 2 O 5 Phase, Li 4 SiO 4 The silicon-based negative electrode material is a pre-lithiation negative electrode material, has high initial coulombic efficiency and reversible capacity, long cycle life and stable processing performance. The ionic liquid can have the functions of a dispersing agent and a grinding aid, and effectively avoids the phenomenon of viscosityAnd the lithium metal with stronger ductility is agglomerated to form powder lumps in the ball milling process, and is adhered to the wall of the ball milling tank, so that the prelithiation of the silicon-based negative electrode material is more uniform, and the initial coulomb efficiency and long cycle stability of the silicon-based negative electrode material are ensured.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium battery materials, and particularly relates to a silicon-based negative electrode material and a preparation method and application thereof.
Background
With the rapid development and popularization of electric automobiles, higher requirements are put forward on the energy density and the cycle life of lithium ion batteries. In the prior art, the graphite cathode material is close to the theoretical capacity, and in order to meet the requirements of new-generation energy, improve the energy density of a battery and develop a new cathode material, the development of the graphite cathode material is urgent. Compared with graphite cathode materials, silicon-based materials are receiving much attention due to their advantages of high theoretical specific capacity, low lithium intercalation/deintercalation potential, wide sources, etc., but their large volume expansion (about 300% for silicon cathodes) and low first coulombic efficiency have hindered their commercial applications.
The pre-lithiation is to supplement lithium in advance before the electrode is circulated, so as to offset irreversible lithium consumption, supplement short plates with low initial coulomb efficiency of the silicon-based negative electrode material and prolong the cycle life; the pre-lithiation technology can effectively improve the first coulombic efficiency and improve the performance of the silicon-based negative electrode material. In the prior art, a pre-lithiated silicon-oxygen negative electrode material is generally prepared by high-temperature sintering, but pre-lithiation is carried out at a high temperature, so that the disproportionation reaction of silicon monoxide is aggravated, inert silicon dioxide is generated, the active capacity of the negative electrode material is reduced, and meanwhile, silicon crystal grains grow up and the cycle performance is deteriorated. In the prior art, lithium is supplemented to the cathode material by adopting an electrochemical principle, but the method has a complex process and is difficult to be applied in a large scale.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the problems of low first efficiency, short cycle life and the like of the pre-lithiation silicon-based negative electrode material prepared in the prior art, so that a silicon-based negative electrode material, and a preparation method and application thereof are provided.
Therefore, the invention provides the following technical scheme.
The invention provides a silicon-based negative electrode material, which comprises a non-metal silicon-containing material, a lithium source and ionic liquid as raw materials;
the melting point of the ionic liquid is lower than that of the lithium metal.
The ionic liquid is tetrabutyl phosphine bis (trifluoromethanesulfonyl) imide salt (C) 18 H 36 F 6 NO 4 PS 2 ) 1-butyl-3-methylimidazolium p-methylbenzenesulfonate (C) 15 H 22 N 2 O 3 S), N-hexylpyridinium hexafluorophosphate (C) 11 H 18 F 6 NP) and N-octylpyridinium Bromide salt (C) 13 H 22 NBr).
The ionic liquid does not react with a lithium source chemically, and the property is stable.
The non-metallic silicon-containing material comprises SiO x And C;
wherein the value range of x is more than or equal to 0 and less than 2;
preferably, the lithium source is lithium foil, lithium sheet or lithium powder;
preferably, the mass fraction of C in the non-metallic silicon-containing material is 2-10%.
The mass ratio of the ionic liquid to the lithium source to the non-metallic silicon-containing material is (1-5): 1: (5-30).
The invention also provides a preparation method of the silicon-based cathode material, which comprises the following steps,
mixing the ionic liquid, the non-metallic silicon-containing material and a lithium source, and performing ball milling;
the temperature of the ball milling is lower than 0 ℃.
The ball milling is carried out at-60 to-20 ℃.
Performing ball milling in a positive and negative alternative ball milling mode;
the time of the positive and negative alternate ball milling is 8-12 min.
The production method satisfies at least one of (1) to (4),
(1) the ball milling is carried out in the liquid nitrogen atmosphere; so as to ensure that the ball milling is carried out under the condition of low temperature;
(2) the rotation speed of the ball mill is 200-600 rpm;
(3) the ball milling time is 1-10 h;
(4) the ball material ratio is (10-40): 1.
during the ball milling process, Li is formed by the lithium source and the non-metallic silicon-containing material 2 SiO 3 Phase, Li 2 Si 2 O 5 Phase, Li 4 SiO 4 At least one of the phases is structured.
In addition, the invention provides a negative pole piece which comprises the silicon-based negative pole material prepared by the preparation method of the claim.
The silicon-based negative electrode material, the conductive agent, the binder and water are uniformly stirred, coated on copper foil, and dried to obtain the negative electrode plate.
The invention also provides a lithium ion battery which comprises the negative pole piece.
The technical scheme of the invention has the following advantages:
1. the silicon-based negative electrode material provided by the invention comprises raw materials of a non-metal silicon-containing material, a lithium source and ionic liquid; the melting point of the ionic liquid is lower than that of the lithium metal. The lithium in the silicon-based negative electrode material is Li 2 SiO 3 Phase, Li 2 Si 2 O 5 Phase, Li 4 SiO 4 The silicon-based negative electrode material is a pre-lithiation negative electrode material, has high initial coulombic efficiency and reversible capacity, long cycle life and stable processing performance. The ionic liquid can have the functions of a dispersing agent and a grinding aid, so that the problems that powder lumps are formed due to agglomeration of metal lithium with high viscosity and high ductility in a ball milling process, the metal lithium is adhered to the wall of a ball milling tank and the like are effectively solved, the pre-lithiation of the silicon-based negative electrode material is more uniform, and the first coulomb efficiency and the long cycle stability of the silicon-based negative electrode material are ensured.
2. The pre-lithiation degree of the silicon-based negative electrode material can be regulated and controlled by controlling the addition of the lithium source, and the silicon-based negative electrode material provided by the invention has good pre-lithiation uniformity and higher reversible capacity and first coulombic efficiency.
3. The preparation method of the silicon-based negative electrode material provided by the invention is characterized in that ball milling is carried out on the raw materials under the low-temperature condition, and Li exists in the obtained silicon-based negative electrode material 2 SiO 3 Phase, Li 2 Si 2 O 5 Phase, Li 4 SiO 4 At least one of the three structures overcomes the problems of disproportionation reaction and the like caused by high-temperature roasting in the prior art, avoids the generation of inert silicon dioxide, and ensures the active capacity, the first coulombic efficiency and the long-term cycling stability of the cathode material.
The invention adopts the traditional ball milling method, leads the material particles to be fractured and cold-welded through the collision between milling balls, reduces the size of the particles or crystal grains, generates certain alloying degree, can prepare the silicon-based cathode material with higher first coulombic efficiency, simultaneously carries out ball milling at low temperature, has low heat, can ensure that the metal lithium is embrittled, is beneficial to the ball milling of the metal lithium, and prevents the problems that the metal lithium forms powder lumps in the ball milling process and adheres to the wall of a ball tank and the like because the metal lithium has unique flexibility and viscosity. Furthermore, the silicon-based negative electrode material prepared by the method has the advantages of high first coulombic efficiency, good long-term cycling stability, long service life and the like.
Furthermore, ball milling is carried out under the low-temperature condition, the granularity of the non-metal silicon-containing material can be reduced, and the cycle performance of the battery is improved. The ball milling is carried out under the low temperature condition, so that the problems of high potential safety hazard, equipment corrosion and the like caused by the fusion state of the lithium metal due to heat release of the ball milling in the ball milling process are solved. The ball milling method has the advantages of simple process, high repeatability and application prospect in large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is an XRD pattern of the silicon-based anode material of example 1 of the present invention;
FIG. 2 is an XRD pattern of a silicon-based anode material in example 2 of the present invention;
FIG. 3 is an XRD pattern of a silicon-based anode material according to example 3 of the present invention;
FIG. 4 is an XRD pattern of a comparative example 1 silicon oxide material of the present invention;
fig. 5 is a first-turn charge-discharge curve of a battery produced from the negative electrode materials provided in examples 1 to 3 in experimental example 2 of the present invention;
fig. 6 is a first-turn charge-discharge curve of a battery produced from the negative electrode materials provided in comparative examples 1 to 2 in experimental example 2 of the present invention;
FIG. 7 shows the cycle characteristics of the battery of test example 2 of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
This example provides a silicon-based negative electrode material, which comprises 2g of tetrabutylphosphonium bis (trifluoromethanesulfonyl) imide salt (C) 18 H 36 F 6 NO 4 PS 2 ) 1g of lithium foil and 20g of commercially available silicon oxide negative electrode material (SiO/C, carbon content in the negative electrode material is 4.5 wt%).
The preparation method of the silicon-based anode material comprises the following steps,
putting the raw materials into a low-temperature planetary ball mill in an argon-protected glove box according to the massPerforming ball milling for 4 hours in a ball milling tank of the machine by adopting a positive and negative alternative ball milling mode to obtain a pre-lithiated silicon-based negative electrode material; wherein, the glove box H 2 O and O 2 The content is less than 0.1 ppm; the ball-material ratio is 20:1, the rotation speed of ball milling is 400rpm, and the time of positive and negative alternation is 10 min; the ball milling is carried out in a planetary ball mill with a heat-insulating cover, wherein a liquid nitrogen gas source is continuously input, and the ball milling temperature is ensured to be about-60 ℃.
Fig. 1 is an XRD pattern of the prelithiated silicon-based anode material provided in this example. As can be seen from FIG. 1, SiO in the silicon oxide material 2 The broad peak disappeared, and Si diffraction peak and Li were also detected 2 Si 2 O 5 The diffraction peak of the phase (PDF standard card diffraction peak atlas, card number 72-0102) shows that the mechanochemical reaction occurs in the ball milling process, and the reaction process is expressed as 3SiO 2 +4Li→Li 2 O+Li 2 Si 2 O 5 + Si, since the highly negative free energy change allows this reaction to occur freely during ball milling, Li is not present in FIG. 1 2 The reason for O is that it is an amorphous structure.
Example 2
This example provides a silicon-based negative electrode material, which comprises 2g of tetrabutylphosphonium bis (trifluoromethanesulfonyl) imide salt (C) 18 H 36 F 6 NO 4 PS 2 ) 1.5g of lithium foil and 20g of commercially available silicon oxide negative electrode material (same as example 1).
The preparation method of the silicon-based anode material comprises the following steps,
putting the raw materials into a ball milling tank of a low-temperature planetary ball mill according to the mass in an argon-protected glove box, and performing ball milling for 4 hours in a positive and negative alternative ball milling manner to obtain a pre-lithiated silicon-based negative electrode material; wherein, the glove box H 2 O and O 2 The content is less than 0.1 ppm; the ball-material ratio is 20:1, the rotation speed of ball milling is 400rpm, and the time of positive and negative alternation is 10 min; the ball milling is carried out in a planetary ball mill with a heat-insulating cover, wherein a liquid nitrogen gas source is continuously input, and the ball milling temperature is ensured to be about-60 ℃.
FIG. 2 is a pre-lithiated silicon-based negative electrode material provided in this exampleXRD pattern of material. As can be seen from FIG. 2, except for Li 2 Si 2 O 5 Outside the phase, small amounts of Li are also formed as the lithium content increases 2 SiO 3 Phase (PDF standard card diffraction peak pattern, card number 74-2145), reaction process is shown as 3SiO 2 +4Li→Li 2 O+Li 2 Si 2 O 5 + Si and 2SiO 2 +4Li→Li 2 O+Li 2 SiO 3 +Si。
Example 3
This example provides a silicon-based negative electrode material, which comprises 2g of tetrabutylphosphonium bis (trifluoromethanesulfonyl) imide salt (C) 18 H 36 F 6 NO 4 PS 2 ) 2g of lithium foil and 20g of commercially available silicon oxide negative electrode material (same as example 1).
The preparation method of the silicon-based anode material comprises the following steps,
putting the raw materials into a ball milling tank of a low-temperature planetary ball mill according to the mass in a glove box protected by argon, and performing ball milling for 4 hours in a positive and negative alternative ball milling manner to obtain a pre-lithiated silicon-based negative electrode material; wherein, the glove box H 2 O and O 2 The content is less than 0.1 ppm; the ball-material ratio is 20:1, the rotation speed of ball milling is 400rpm, and the time of positive and negative alternation is 10 min; the ball milling is carried out in a planetary ball mill with a heat-insulating cover, wherein a liquid nitrogen gas source is continuously input, and the ball milling temperature is ensured to be about-60 ℃.
Fig. 3 is an XRD pattern of the prelithiated silicon-based anode material provided in this example. As can be seen from FIG. 3, as the lithium content increases, Li 2 SiO 3 Increase phase, and Li is generated in the ball milling process 2 SiO 3 Phase and Li 2 Si 2 O 5 By controlling the amount ratio of lithium to silicon oxide materials, the phase structure and abundance of the silicate formed can be controlled.
Example 4
This example provides a silicon-based negative electrode material, which comprises 3g of 1-butyl-3-methylimidazolium p-methylbenzenesulfonate (C) 15 H 22 N 2 O 3 S), 1g of lithium foil and 5g of commercially available silicon oxide negative electrode material (same as above)Example 1).
The preparation method of the silicon-based anode material comprises the following steps,
putting the raw materials into a ball milling tank of a low-temperature planetary ball mill according to the mass in an argon-protected glove box, and performing ball milling for 6 hours in a positive and negative alternative ball milling manner to obtain a pre-lithiated silicon-based negative electrode material; wherein, the glove box H 2 O and O 2 The content is less than 0.1 ppm; the ball-material ratio is 30:1, the rotation speed of ball milling is 400rpm, and the time of positive and negative alternation is 10 min; the ball milling is carried out in a planetary ball mill with a heat-insulating cover, wherein a liquid nitrogen gas source is continuously input, and the ball milling temperature is ensured to be about-60 ℃.
Comparative example 1
This comparative example provides a negative electrode material, and a commercially available silicon oxide material (same as example 1) is used as the negative electrode material, and the XRD pattern of the commercially available silicon oxide material is shown in fig. 4.
Comparative example 2
This comparative example provides a negative electrode material differing from example 1 by the elimination of the ionic liquid tetrabutylphosphonium bis (trifluoromethanesulfonyl) imide salt (C) 18 H 36 F 6 NO 4 PS 2 ) The raw materials include lithium foil and commercially available silicon oxide material (same as example 1), and the preparation method is the same as example 1.
Test example 1
The test example provides the performance of the anode materials provided in each example and comparative example, specifically as follows,
the particle size of the negative electrode materials of the examples and the comparative examples was measured by a laser particle sizer, and the results are shown in table 1; meanwhile, whether agglomeration, caking and other phenomena occur in the process of preparing the obtained cathode material is observed, and the result is shown in table 1;
TABLE 1 Performance results for example and comparative anode materials
| Examples of the invention | Particle size (D) 50 ，μm) | Whether the agglomeration phenomenon occurs in the preparation process |
| Example 1 | 3.8 | Without agglomeration |
| Example 2 | 3.7 | Without agglomeration |
| Example 3 | 4.1 | Without agglomeration |
| Example 4 | 3.3 | Without agglomeration |
| Comparative example 1 | 7.1 | / |
| Comparative example 2 | 5.3 | Agglomeration |
Note: comparative example 1 in table 1 is a commercially available carbon dioxide material, free of agglomeration and is indicated by "/".
The results in table 1 show that the problems of agglomeration, caking and the like are not easy to occur when the negative electrode material is prepared, and the particle size of the negative electrode material prepared by the invention is small.
Test example 2
The experimental example provides performance tests of the negative electrode materials provided in the examples and the comparative examples in a lithium ion battery, and specifically as follows,
preparing a negative pole piece: the negative electrode material provided by each embodiment and comparative example is used as an active substance, polyacrylic acid (PAA) is used as a binder, small-particle conductive carbon black (Super P) is used as a conductive agent, the mass ratio of the active substance to the conductive agent to the binder is 7:1.5:1.5, the PAA with the mass is added into deionized water to be uniformly dispersed, then the conductive agent is added, the active substance is added after uniform dispersion, the active substance is coated on a copper foil, the copper foil is dried at 60 ℃ and then sliced, and then the slice is placed in a vacuum blast oven to be dried at 110 ℃ to obtain the negative electrode piece of the lithium ion battery.
Preparing a battery: a metal lithium sheet is used as a counter electrode, PP/PE is used as a diaphragm, and 1M LiPF 6 The battery is characterized in that the EC + DEC + DMC is used as electrolyte, wherein EC is ethylene carbonate, DEC is diethyl carbonate, DMC is dimethyl carbonate, the volume ratio of EC, DEC and DMC is 1:1:1, and a 2025 button cell is assembled in a glove box filled with argon.
The performance of the battery is tested by adopting a BT2011 type blue tester of Wuhan blue electricity company, and the test procedure is as follows: 0.1C was discharged to 5mV, 0.05C was discharged to 5mV, 0.02C was discharged to 5mV, 0.01C was discharged to 5mV, and the latter 0.1C was charged to 1.5V, with the results shown in FIGS. 5-7.
Fig. 5 to 6 are first-turn charge and discharge curves of the respective batteries. As can be seen from fig. 5, the first-turn coulombic efficiencies ICE of the batteries prepared from the negative electrode materials provided in examples 1 to 3 reached 90.3%, 89.1% and 89.38%, respectively, and the capacities were 1425.1, 1442.5 and 1362.9mAh/g, respectively. As can be seen from fig. 6, the first-turn coulombic efficiency of the battery made of the negative electrode material in comparative example 1 is only 75.2%, and the first-turn coulombic efficiency of the battery made of the negative electrode material in comparative example 2 is only 83.1%, which indicates that the negative electrode material provided by the present invention has a higher first-turn coulombic efficiency when used in a battery.
Fig. 7 is a cycle performance graph of each battery. As can be seen from fig. 7, the batteries prepared from the negative electrode materials provided in examples 1 to 3 have better cycle stability, and the capacity retention rates after 30 cycles are 97.8, 78.7% and 86.3%, respectively, while the capacity retention rate after 30 cycles of the battery prepared from the negative electrode material in comparative example 1 is only 38.8%, and the capacity retention rate after 30 cycles of the battery prepared from the negative electrode material in comparative example 2 is only 73.5%, which indicates that the negative electrode material provided by the invention has better cycle stability when used in the battery, and the batteries prepared in comparative examples 1 and 2 have poor cycle stability and short service life.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The silicon-based negative electrode material is characterized in that raw materials comprise a non-metal silicon-containing material, a lithium source and ionic liquid;
the melting point of the ionic liquid is lower than that of the lithium metal.
2. The silicon-based anode material of claim 1, wherein the ionic liquid is at least one of tetrabutylphosphonium bis (trifluoromethanesulfonyl) imide salt, 1-butyl-3-methylimidazolium p-methylbenzenesulfonate, N-hexylpyridinium hexafluorophosphate and N-octylpyridinium bromide salt.
3. The silicon-based anode material according to claim 1 or 2, wherein the non-metallic silicon-containing material comprises SiO x And C;
wherein the value range of x is more than or equal to 0 and less than 2;
preferably, the lithium source is lithium foil, lithium sheet or lithium powder;
preferably, the mass fraction of C in the non-metallic silicon-containing material is 2-10%.
4. The silicon-based anode material according to any one of claims 1 to 3, wherein the mass ratio of the ionic liquid to the lithium source to the non-metallic silicon-containing material is (1-5): 1: (5-30).
5. A preparation method of a silicon-based negative electrode material is characterized by comprising the following steps,
mixing the ionic liquid, the non-metallic silicon-containing material and a lithium source, and performing ball milling;
the temperature of the ball milling is lower than 0 ℃.
6. The method of claim 5, wherein the ball milling is performed at-60 to-20 ℃.
7. The method according to claim 5 or 6, wherein the ball milling is performed by a positive and negative alternative ball milling method;
the time of the positive and negative alternate ball milling is 8-12 min.
8. The production method according to any one of claims 5 to 7, characterized in that at least one of (1) to (4) is satisfied,
(1) the ball milling is carried out in the liquid nitrogen atmosphere;
(2) the rotation speed of the ball mill is 200-600 rpm;
(3) the ball milling time is 1-10 h;
(4) the ball material ratio is (10-40): 1.
9. a negative pole piece is characterized by comprising the silicon-based negative pole material prepared by the preparation method of any one of claims 5 to 8.
10. A lithium ion battery comprising the negative electrode sheet of claim 9.
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