CN109755515B - Silicon/carbon cathode composite material of lithium ion battery and preparation method thereof - Google Patents
Silicon/carbon cathode composite material of lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silicon/carbon cathode composite material of a lithium ion battery, which has a core-shell structure, wherein an inner core is silicon particles with a porous structure, a shell layer is a coiled carbon nanotube cluster with a large number of gaps, and the interfaces of the two are connected by metal silicide. In the invention, the porosity of the silicon particles obviously relieves the volume expansion of silicon in the charging and discharging processes, and improves the diffusion performance of lithium ions in the silicon; the carbon nanotube cluster has high conductivity, overcomes the defect of low electronic conductivity of silicon, and is used as a flexible external buffer layer to further relieve the volume expansion of the silicon; the metal silicide is used as a tight connection point, an electron transmission channel is constructed between the silicon and the carbon nano tube, and the carbon nano tube can be prevented from falling off in the charging and discharging process. The silicon/carbon cathode composite material with the novel structure provided by the invention has the advantages of high specific capacity, good cycle performance, excellent rate performance and the like in the application of lithium ion batteries, and is low in preparation cost, simple in method and easy to realize industrial production.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a lithium ion battery silicon/carbon cathode composite material with a novel structure and a preparation method thereof.
Background
The lithium ion battery has the performance advantages of high energy density, high working voltage, high charging speed, long cycle life, environmental friendliness, safety and stability, is a green energy storage power supply with the greatest development prospect at present, and is widely applied to the fields of mobile electronic equipment, electric automobiles and electronics. However, with the development requirements of miniaturization, high energy and portability of electronic and electric appliances and the popularization and application of new energy electric vehicles, the requirements on various technical indexes of lithium ion batteries are higher and higher.
The currently commonly used lithium ion battery cathode material is graphite, and the theoretical specific capacity of the graphite is only 372mAhg-1The application requirements of the current lithium ion battery on high specific capacity and high power cannot be met, and the development of novel high-performance negative electrode materials is urgent. The theoretical specific capacity of the silicon negative electrode material is about 10 times of that of graphite materials and is up to 3580mAh g-1The material is known to be the material with the highest theoretical specific capacity for the lithium battery negative electrode, has rich resources and low price, is one of ideal candidate materials for replacing graphite negative electrode materials, but the material has the following problems in the practical application process: 1) silicon can have severe volume change (the volume expansion reaches 300-; 2) the diffusion coefficient of lithium in a silicon material is small; 3) silicon materials have poor electronic conductivity. The above problems have hindered the practical application of silicon materials in lithium ion batteries.
In order to overcome the disadvantages of volume expansion of silicon material during charging and low diffusion coefficient of lithium in silicon, the prior art solutions mainly focus on developing porous silicon material, including constructing open pore structure metal (such as Cu, Ni, Cu-Al-Fe) and carbon foam skeleton-supported silicon, non-filling coating (such as conductive metal, carbon, TiO)2, SiO x ) Coated silicon, nano silicon with gap or hole structure (nano silicon material with nano wire cluster, hollow ball, pomegranate-shaped, tubular or eggshell structure), etc. [1-3]. However, the mesoporous structure in silicon materials is currently mainly constructed by acid or alkali etching of inorganic templating agents (SiO) x ，NiO，CaCO3And Mg, Fe alloy) and thermally decomposed organic template agent (polymethyl methacrylate (PMMA), Polyacrylonitrile (PAN) and various surfactants, etc.) [4-5 ]]. However, in these conventional pore-forming methods, the use of a template agent not only increases the preparation cost, but also requires strong corrosive concentrated acid or concentrated alkali (HF or NaOH) treatment, which pollutes the environment. Therefore, the developed pore channel structure is constructed by adopting a template-free preparation method, and the method is used for green and economic synthesis of the commercialized porous silicon-based composite materialThe composite material is of considerable importance. In addition, at present, articles and patents on preparation of lithium ion battery silicon negative electrode materials by using perlite as a raw material are rarely reported, and perlite is mainly concentrated in application fields such as building heat preservation and industrial heat preservation at present. The application field of the perlite material is expanded and deepened, so that the perlite material becomes a silicon cathode material with high performance and high cost performance, and the silicon cathode material is applied to the field of new energy lithium ion batteries and is expected to generate great social benefit and economic benefit.
In addition, carbon-coated silicon materials, in which the carbon coating has both filled and unfilled forms [6-7], are effective measures against the poor electron conductivity of silicon electrodes. The filled carbon coating layer can improve the electronic conductivity, but the elasticity or ductility of the carbon coating layer is insufficient, so that the internal tension caused by the silicon material in the charging and discharging process cannot be effectively reduced, the electrode structure is easy to collapse, and the cycle life is shortened; the non-filling carbon coating layer can effectively relieve the volume expansion of silicon due to the existence of the internal void structure, but the contact area between the silicon and the carbon is correspondingly reduced due to the large number of void structures existing between the silicon and the carbon, and the electronic/ionic conductivity of the carbon coating layer is reduced.
Therefore, the silicon/carbon cathode composite material structure which can relieve the volume expansion of silicon and has stronger ion/electron conductivity is constructed, and the application requirements of high specific capacity, high rate capability and high stability of the lithium ion battery can be met.
Disclosure of Invention
The invention provides a silicon/carbon negative electrode composite material of a lithium ion battery and a preparation method thereof, aiming at overcoming three main problems of volume expansion of a silicon material, slow diffusion of lithium ions in the silicon material and poor electronic conductivity of silicon in the charging and discharging process and improving the specific discharge capacity, the charging and discharging cycle stability and the rate capability of the silicon-based negative electrode material.
The purpose of the invention is realized as follows:
the silicon/carbon cathode composite material of the lithium ion battery is characterized in that: the composite material has a core-shell structure, wherein the core is porous silicon particles, the shell is a coiled carbon nanotube cluster winding layer with a large number of gap structures, and the carbon nanotube cluster winding layer are riveted and connected through metal silicide; wherein, the porous silicon particles are prepared by using perlite as a raw material;
in the silicon/carbon cathode composite material for the lithium ion battery, the metal silicide is any one of nickel silicide, cobalt silicide and iron silicide.
In the lithium ion battery silicon/carbon cathode composite material, the average particle size of porous silicon is between 5 and 50 mu m, the size of internal pores is between 400 and 1000 nm, and the thickness of a silicon wall is between 50 and 200 nm;
in the silicon/carbon cathode composite material of the lithium ion battery, the length of the carbon nano tube is between 5 and 15 mu m, the tube diameter is between 50 and 300 nm, and the thickness of the carbon wall is between 2 and 20 nm.
In the lithium ion battery silicon cathode composite material, the porous silicon material accounts for 30-60% of the total mass, and the carbon nanotube material and the metal silicide account for 40-70% of the total mass according to the mass percentage.
In the lithium ion battery silicon/carbon cathode composite material, the porosity of the silicon particles obviously relieves the volume expansion of silicon in the charging and discharging processes, and improves the diffusion performance of lithium ions in the silicon; the carbon nanotube cluster has high conductivity, overcomes the defect of low electronic conductivity of silicon, and is used as a flexible external buffer layer to further relieve the volume expansion of the silicon; the metal silicide is used as a tight connection point, an electron transmission channel is constructed between the silicon and the carbon nano tube, and the carbon nano tube can be prevented from falling off in the charging and discharging process. The silicon/carbon cathode composite material with the novel structure provided by the invention has the advantages of high specific capacity, good cycle performance, excellent rate capability and the like in the application of lithium ion batteries.
The preparation method of the silicon/carbon cathode composite material of the lithium ion battery comprises the following steps:
1) ball milling is carried out for 48 hours by taking perlite as a raw material;
2) preheating, quickly heating at high temperature and quickly cooling the material treated in the step 1), and performing aftertreatment by using acid liquor to obtain a porous silicon dioxide material;
3) carrying out metal thermal reduction treatment on the material treated in the step 2) in a high-temperature inert atmosphere, and carrying out post-treatment by using acid liquor to obtain a porous silicon material;
4) and (3) uniformly mixing the material treated in the step 3) with metal acetate (or metal oxalate) and hydrocarbon, and roasting in a high-temperature inert atmosphere to obtain the silicon/carbon cathode composite material of the lithium ion battery.
In the above preparation method, the step 2) comprises the steps of: first at 200oC ～ 400oPreheating in C for 20-30 min, then 1000oC ～ 1200oC, heating for 2-20 s at high temperature, and finally quickly transferring the material from the high-temperature environment to 20oC～ 35oCooling at C temperature, and adding 3-5M hydrochloric acid at 60 deg.CoC~ 100oAnd C, treating for 24 hours to obtain the porous silica material.
In the above production method, the step 3) comprises the following steps; mixing the material obtained in step 2) with magnesium powder at 650oC ～ 750oCarrying out a magnesiothermic reduction reaction at the high temperature of C and in Ar atmosphere, and then treating for 4h by adopting 0.5-2M hydrochloric acid to obtain the porous silicon material.
In the above preparation method, the step 4) comprises the steps of: mixing the material obtained in step 3) with metal acetate (or metal oxalate), hydrocarbon, etc. at 650oC ～ 750oHigh temperature of C and Ar or N2And roasting in the atmosphere to obtain the silicon/carbon cathode composite material of the lithium ion battery.
Further, the metal acetate or metal oxalate in the step 4) is nickel acetate, cobalt acetate or ferrous oxalate; the hydrocarbon is melamine, urea or dicyandiamide.
Further, the metal acetate in the step 4) is nickel acetate; the hydrocarbon is melamine.
Has the positive and beneficial effects that: the silicon/carbon cathode composite material prepared by the invention is novel in structure and has a core-shell structure, the inner core is porous silicon particles, and the pore volume of the silicon material is 4-6 times of the volume of a silicon wall, so that the volume expansion of the silicon in the charge and discharge process can be self-regulated and buffered, and the charge and discharge cycle stability of the silicon material is improved; the invention develops the silicon-based negative electrode composite material of the lithium ion battery by taking the perlite as the raw material, and has the application advantage of high cost performance. In addition, the whole process does not need to use expensive silicon precursors and templates, the preparation cost is low, the process is simple, the industrial production of the silicon-based negative electrode composite material is easy to realize, and the large-scale application requirements of the lithium ion battery can be met.
Drawings
FIG. 1 is a scanning electron microscope image of a porous silicon material prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the silicon/carbon negative electrode composite material prepared in example 1 of the present invention;
fig. 3 is a graph showing the first charge and discharge properties of the silicon/carbon anode composite material prepared in example 1 of the present invention;
fig. 4 shows the charge-discharge cycle stability of 500 times of the silicon/carbon negative electrode composite material prepared in example 1 of the present invention;
fig. 5 is a graph showing rate capability of the silicon/carbon anode composite material prepared in example 1 of the present invention.
Detailed Description
The invention will be further described with reference to specific examples:
example 1
(1) The method is characterized in that perlite is used as a raw material, the perlite is placed in a 100ml agate ball milling tank, and 50g of agate balls with the diameter of 20mm, 40g of agate balls with the diameter of 10mm and 10g of agate balls with the diameter of 5mm are added. Wherein the mass ratio of the agate balls to the perlite is 20:1, the ball milling speed is 450 rpm, and the ball milling is carried out for 48 hours, so that the micron-sized perlite particles are obtained.
(2) At 300oC preheat for 25 min, then 1100oC, heating for 10s, and finally quickly transferring the material to 25 ℃ from the high-temperature environmentoCooling at room temperature, and adding 4M hydrochloric acid at 80 deg.CoAnd C, treating for 24 hours, cleaning, filtering and drying to obtain the porous silicon dioxide material.
(3) Will be provided with10g of porous silica was mixed with 10g of magnesium powder at 700 goPerforming a magnesiothermic reduction reaction under the atmosphere of C and Ar, and then performing a reaction on the reaction product by using 1M hydrochloric acid at 80 DEG CoAnd C, treating for 4h to obtain the porous silicon material.
(4) 3g of porous silicon material, 3.2g of nickel acetate and 7.5g of melamine are mixed uniformly and are mixed at 700 DEGoAnd C and Ar are roasted to obtain the silicon/carbon cathode composite material of nickel silicide connected carbon nano tube and porous silicon. In the composite material, the porous silicon material accounts for 45.1 of the total mass of the composite materialwt%。
Mixing a silicon/carbon anode composite material: carbon black: mixing polyacrylic acid according to the mass ratio of 8:1:1, taking N-methyl pyrrolidone as solvent, preparing slurry, coating the slurry on the surface of the copper foil, and drying at 120 ℃ for 24 hours to prepare the working electrode slice. The counter electrode is a lithium plate, and the electrolyte is 1.0M LiPF6EC (ethylene carbonate) DMC (dimethyl carbonate) =1:1 (C:)V/V)/10wt% FEC (fluoroethylene carbonate). The button cell (CR 2032) was assembled in a high purity argon glove box. A Land battery tester is used for carrying out constant current charge and discharge tests to research the charge and discharge specific capacity and the cycle performance of the silicon/carbon negative electrode composite material. Voltage test range: 0.01-2.0V: (vsLi/Li+)。
As shown in figure 1, the porous silicon material prepared by the method of the invention takes perlite as a raw material and has a rich macroporous structure, the pore size is distributed at 600-900 nm, the thickness of the silicon wall is 100-150 nm, the volume ratio of the pore to the wall is about 6, which is nearly twice of the volume of the lithium-embedded silicon material (the volume expansion of the lithium-embedded silicon is about 300-400 percent), the volume expansion of the silicon in the charge-discharge process can be overcome, and the charge-discharge cycle stability of the silicon material is improved.
As seen from fig. 2, the morphology of the silicon/carbon negative electrode composite is porous silicon particles with carbon nanotubes entangled, and the carbon tubes and the porous silicon are connected by nickel silicide generated at the interface. The novel structure can ensure that the silicon/carbon negative electrode composite material has good electronic conductivity, ion diffusivity and structural stability, thereby showing excellent charge-discharge performance, rate capability and cycling stability in the application of the lithium ion battery.
As shown in FIG. 3, when the charge-discharge test is performed at 358mA/g (0.1C), the first discharge capacity and the charge specific capacity of the silicon/carbon negative electrode composite material are 2418 mAh g respectively-1And 1956 mAh g-1The coulombic efficiency was 80.9%. After 100 charge-discharge cycles, the average coulombic efficiency reached 99.7%.
As shown in FIG. 4, after the silicon/carbon negative electrode composite material is subjected to charge-discharge cycling for 500 times under 358mA/g (0.1C), the specific discharge capacity of the silicon/carbon negative electrode composite material is still as high as 1547mAhg-1The capacity retention rate was 99.5%, and high charge-discharge cycle stability was exhibited. As seen in FIG. 5, the mA g was 716 (0.2C), 1790 (0.5C), 3580 (1C) and 7160 (2C)-1After charging and discharging for 100 weeks, the specific discharge capacity of the silicon/carbon negative electrode composite material is 1365, 1176, 974 and 778 mAh g-1And exhibits excellent charge/discharge rate performance.
Example 2
Step (1-3) the same as the preparation process of example 1, in step (4), 3g of porous silicon material was uniformly mixed with 3.5 g of cobalt acetate and 7.6 g of dicyandiamide, and the mixture was subjected to a mixing process of 700 goAnd C and Ar atmosphere roasting to obtain the cobalt silicide connected carbon nanotube and porous silicon/carbon cathode composite material. In the composite material, the porous silicon material accounts for 43.2 of the total mass of the composite materialwt% of the total weight of the composition. The electrochemical properties of the composite material are shown in table 1.
Example 3
Step (1-3) the same procedure as in example 1 was followed, and in step (4), 3g of the porous silica material was uniformly mixed with 3.2g of ferrous oxalate and 7.6 g of urea, and the mixture was further processed at 700 deg.CoAnd C and Ar are roasted to obtain the silicon/carbon cathode composite material of iron silicide connected with the carbon nano tube and the porous silicon. In the composite material, the porous silicon material accounts for 40.6 of the total mass of the composite materialwt% of the total weight of the composition. The electrochemical properties of the composite material are shown in table 1.
TABLE 1 Charge and discharge Properties of silicon/carbon negative electrode composites in examples
The above table shows that the silicon/carbon negative electrode composite material has high specific discharge capacity and excellent cycling stability, the capacity retention rate is more than 91% after 500 cycles, the problem of poor cycling performance of the existing silicon negative electrode material is solved, and the application requirements of the high-performance and high-stability lithium ion battery are further met.
In the preparation method, perlite with rich reserves is used as a raw material, firstly, micron-level perlite particles are obtained through ball milling, a porous structure is constructed through further heat treatment of crystal water in volatile materials, the shape of a hole is fixed through rapid cooling treatment, expanded perlite with the porous structure is obtained, and then, acid treatment is carried out, so that the silicon dioxide material with the porous structure is obtained. And then carrying out metallothermic reduction and acid treatment on the porous silicon dioxide to obtain the silicon material with a porous structure. And finally, adopting metal acetate (or metal oxalate) and hydrocarbon as precursors, and utilizing the tail end of transition metal (Ni, Co, Fe) to catalyze the growth mechanism of the carbon nano tube in the high-temperature roasting process to generate the carbon nano tube material with the top end embedded with the transition metal. And the transition metal (Ni, Co, Fe) embedded in the carbon nano tube can further generate metal silicide with the porous silicon particles through alloying reaction, so that the carbon nano tube coating layer is firmly connected with the porous silicon particles, and finally the high-performance lithium ion battery silicon/carbon cathode composite material is prepared. The preparation method is low in cost, simple in preparation process, economic and environment-friendly, is very suitable for large-scale industrial production, and is expected to accelerate the commercial application of the silicon-based negative electrode material in the lithium ion battery.
The prepared silicon/carbon cathode composite material can be characterized by adopting the following method: mixing the prepared silicon/carbon negative electrode composite material, carbon black or graphite powder, polyacrylic acid or polyvinylidene fluoride or acid methyl cellulose according to the mass ratio of 8:1:1, making slurry, coating the slurry on the surface of copper foil, drying at 120 ℃, punching to prepare a negative electrode sheet, using a lithium sheet as a counter electrode, and assembling the negative electrode sheet into a button cell in a high-purity argon glove box. The prepared silicon/carbon cathode composite material is applied to a lithium ion battery, and shows high mass specific capacity, good charge-discharge cycle performance and rate capability.
In addition, the invention takes perlite as raw material, and the developed silicon-based negative electrode composite material of the lithium ion battery has the application advantage of high cost performance. In addition, the whole process does not need to use expensive silicon precursors and templates, the preparation cost is low, the process is simple, the industrial production of the silicon-based negative electrode composite material is easy to realize, and the large-scale application requirements of the lithium ion battery can be met.
The silicon/carbon cathode composite material prepared by the invention is novel in structure and has a core-shell structure, the inner core is porous silicon particles, and the pore volume of the silicon material is 4-6 times of the volume of a silicon wall, so that the volume expansion of the silicon in the charge and discharge process can be self-regulated and buffered, and the charge and discharge cycle stability of the silicon material is improved;
the porosity of the silicon particles obviously improves the diffusion performance of lithium ions in silicon, increases the contact active specific surface area of the material and the utilization rate of the material, and is favorable for improving the lithium storage specific capacity and the rate capability of the silicon/carbon cathode composite material.
The carbon nanotube cluster is used as an external flexible winding layer, a spongy buffer layer is formed on the surface of a silicon material, and a developed gap structure formed by the carbon nanotube cluster further buffers the volume expansion of silicon. Meanwhile, the high conductivity of the carbon nano tube overcomes the defect of low electronic conductivity of the silicon semiconductor material, and enhances the electronic transmission capability of the silicon/carbon cathode composite material.
The metal silicide in the invention is used as a firm connection point of the carbon nano tube and the silicon particles, a rapid electronic transmission channel is constructed between the silicon and the carbon nano tube, the carbon nano tube can be prevented from falling off due to the volume change of the silicon in the charging and discharging processes, and the electronic transmission capability and the cycling stability of the silicon/carbon cathode composite material are further improved.
According to the preparation method, a silicon precursor, a pore structure template and the like which are expensive are not needed, the template-free preparation method is directly adopted, the perlite with rich reserves is adopted as a raw material, and the physical and chemical deep processing treatment is carried out on the perlite, so that the high added value development and utilization of the perlite material are realized, and the high-performance and high-cost-performance lithium ion battery silicon/carbon negative electrode composite material is developed. In addition, the preparation method has low cost and simple process, and is easy to realize large-scale industrial production.
Finally, it is noted that the above-mentioned embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (3)
1. The silicon/carbon cathode composite material of the lithium ion battery is characterized in that: the composite material has a core-shell structure, wherein the core is porous silicon particles, the shell is a coiled carbon nanotube cluster winding layer with a large number of gap structures, and the carbon nanotube cluster winding layer are riveted and connected through metal silicide; wherein, the porous silicon particles are prepared by using perlite as a raw material; in the lithium ion battery silicon/carbon cathode composite material, the porosity of the silicon particles obviously relieves the volume expansion of silicon in the charging and discharging processes, and improves the diffusion performance of lithium ions in the silicon; the carbon nanotube cluster has high conductivity, overcomes the defect of low electronic conductivity of silicon, and is used as a flexible external buffer layer to further relieve the volume expansion of the silicon; the metal silicide is used as a tight connection point, an electron transmission channel is constructed between the silicon and the carbon nano tube, and the carbon nano tube can be prevented from falling off in the charging and discharging process;
in the lithium ion battery silicon/carbon cathode composite material, the metal silicide is any one of nickel silicide, cobalt silicide and iron silicide; in the lithium ion battery silicon/carbon cathode composite material, the average particle size of porous silicon is between 5 and 50 mu m, the size of internal pores is between 400 and 1000 nm, and the thickness of a silicon wall is between 50 and 200 nm; in the silicon/carbon cathode composite material of the lithium ion battery, the length of the carbon nano tube is between 5 and 15 mu m, the tube diameter is between 50 and 300 nm, and the thickness of the carbon wall is between 2 and 20 nm; in the lithium ion battery silicon cathode composite material, according to the mass percentage, the porous silicon material accounts for 30-60% of the total mass, and the carbon nanotube material and the metal silicide account for 40-70% of the total mass;
the preparation method of the silicon/carbon cathode composite material of the lithium ion battery comprises the following steps:
1) ball milling is carried out for 48 hours by taking perlite as a raw material;
2) preheating, quickly heating at high temperature and quickly cooling the material treated in the step 1), and performing aftertreatment by using acid liquor to obtain a porous silicon dioxide material;
3) carrying out metal thermal reduction treatment on the material treated in the step 2) in a high-temperature inert atmosphere, and carrying out post-treatment by using acid liquor to obtain a porous silicon material;
4) uniformly mixing the material treated in the step 3) with metal acetate or metal oxalate and hydrocarbon, and roasting in a high-temperature inert atmosphere to obtain a silicon/carbon cathode composite material of the lithium ion battery;
in the above preparation method, the step 4) comprises the steps of: mixing the material obtained in step 3) with metal acetate or metal oxalate and hydrocarbon uniformly at 650oC ～ 750oHigh temperature of C and Ar or N2Roasting in the atmosphere to obtain the silicon/carbon cathode composite material of the lithium ion battery; the metal acetate or metal oxalate in the step 4) is nickel acetate, cobalt acetate or ferrous oxalate; the hydrocarbon is melamine, urea or dicyandiamide.
2. The silicon/carbon anode composite material of the lithium ion battery according to claim 1, wherein: in the above preparation method, the step 2) comprises the steps of: first at 200oC ～ 400oPreheating in C for 20-30 min, then 1000oC ～ 1200oC, heating for 2-20 s at high temperature, and finally quickly transferring the material from the high-temperature environment to 20oC～ 35oCooling at CThen using 3-5M hydrochloric acid at 60oC～ 100oAnd C, treating for 24 hours to obtain the porous silica material.
3. The silicon/carbon anode composite material of the lithium ion battery according to claim 1, wherein: in the above production method, the step 3) comprises the following steps; mixing the material obtained in step 2) with magnesium powder at 650oC ～750oCarrying out a magnesiothermic reduction reaction at the high temperature of C and in Ar atmosphere, and then treating for 4h by adopting 0.5-2M hydrochloric acid to obtain the porous silicon material.
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| CN112151760A (en) * | 2020-09-27 | 2020-12-29 | 溧阳天目先导电池材料科技有限公司 | Silicon-based negative electrode composite material and lithium secondary battery |
| CN113363437A (en) * | 2021-05-18 | 2021-09-07 | 恒大新能源技术(深圳)有限公司 | Silicon-based negative electrode material and preparation method thereof, negative plate and secondary battery |
| CN116364869A (en) * | 2021-12-28 | 2023-06-30 | 贝特瑞新材料集团股份有限公司 | Composite negative electrode material, preparation method thereof and lithium ion battery |
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