CN109755522A - A kind of lithium ion battery high-energy density and high power density negative electrode material and preparation method - Google Patents
A kind of lithium ion battery high-energy density and high power density negative electrode material and preparation method Download PDFInfo
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Abstract
The present invention provides a kind of lithium ion battery high-energy densities and high power density negative electrode material, the negative electrode material is " Kiwi berry " structure, " Kiwi berry " core is soft carbon matrix, " Kiwi berry " seed is the nano silicon material for being dispersed in soft carbon matrix surface, " Kiwi berry " pulp is the carbon nanotube for being dispersed in soft carbon matrix and nanometer silicon face, and " Kiwi berry " crust is conductive carbon coating layer.Meanwhile the present invention provides the preparation methods of above-mentioned negative electrode material.Composite negative pole material prepared by the present invention has synergistic effect, can effectively make up the low tapped density of soft carbon and the circulation expansion issues of silicon.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative, and in particular to a kind of lithium ion battery negative material and
Preparation method, especially lithium ion battery high-energy density and high power density composite negative pole material.
Background technique
With the continuous deterioration in short supply with climatic environment of global petroleum resources, develop the new-energy automobile of clean energy-saving by
To the great attention of countries in the world.The development of new-energy automobile, key is in its electrical source of power.Currently, commercialized lithium-ion electric
Pond mainly uses graphite negative electrodes material, but its theoretical specific capacity is only 372mAh/g, and power density is lower, Wu Faman
Demand of the foot future lithium ion battery to high-energy density and high power density.So exploitation high-performance novel electrode material becomes
Research emphasis, soft carbon class negative electrode material is because having irregular Turbostratic, therefore its fast charging and discharging performance, cycle performance and peace
It has excellent performance entirely, but soft carbon energy density is lower.Silicon has the theoretical specific capacity (4200mAh/g) of superelevation and lower de- lithium electric
Position (< 0.5V), and the voltage platform of silicon is slightly above graphite, in charging, difficulty causes surface to analyse lithium, and security performance is more preferable, and silicon becomes
One of potential selection of the richness that the carbon-based cathode of lithium ion battery is regenerated, but the power density of silicon is lower.
Summary of the invention
The present invention is for overcome the deficiencies in the prior art, to provide a kind of lithium ion battery high-energy density and high power
Density negative electrode material and preparation method thereof.
The present invention is achieved by the following technical programs:
A kind of lithium ion battery high-energy density and high power density negative electrode material, the high-energy density and high power density
Negative electrode material is " Kiwi berry " structure, and " Kiwi berry " structure includes " Kiwi berry " core, " Kiwi berry " seed, " Kiwi berry " pulp
" Kiwi berry " crust, " Kiwi berry " core are soft carbon matrix, and " Kiwi berry " seed is to be dispersed in soft carbon matrix table
The nano silicon material in face, " Kiwi berry " pulp are the carbon nanotube for being dispersed in soft carbon matrix and nanometer silicon face, institute
" Kiwi berry " crust is stated as conductive carbon coating layer.
Further, the soft carbon matrix is 2500 DEG C or more graphitisable amorphous carbon materials, and partial size is 4-9 μm.
The soft carbon matrix is a kind or at least two kinds of of group in petroleum coke, needle coke, carbon fiber and non-graphitized carbonaceous mesophase spherules
It closes.
Further, the nano silicon material be polysilicon, monocrystalline silicon, amorphous silicon, preferably, monodispersed monocrystalline silicon or
Polycrysalline silcon；Preferably, the middle partial size of the nano silicon material is 10 ~ 100nm.
Further, the carbon nanotube be single wall or multi wall, caliber 5-50nm, 100nm-5 μm of length；
Further, the conductive carbon coating layer is cracking carbon material.Preferably, the cracking carbon is organic cracking carbon, excellent
1 kind or at least two kinds of of combination being selected as in pitch, carbohydrate and high molecular material, further preferably pitch, phenolic resin, ring
Oxygen resin, polyvinyl alcohol, polyethylene glycol, polyacrylonitrile, a kind in polyethylene oxide or at least two combination.
A kind of preparation method of lithium ion battery high-energy density and high power density negative electrode material, including following step
It is rapid:
A1, nano-silicon surface modification:
Silane coupling agent is added in the flask of alcohol system nano-silicon slurries and is mixed, the silane coupling agent and alcohol system nano-silicon
The mixing mass ratio of slurries is 1:5 ~ 1:50, is then placed in progress ultrasound 2-10h, supersonic frequency in ultrasonic cleaner and is adjusted to
30-120kHz finally obtains the nano-silicon solution being dispersed in alcohol system system；It is modified that surface is formed in nanometer silicon face
Layer, so as to compound with carbon nanotube in second step；
Preferably, the alcohol system medium in the alcohol system nano-silicon slurries is methanol, ethyl alcohol, ethylene glycol, propyl alcohol, isopropanol, 1,2-
1 kind in propylene glycol, glycerine, n-butanol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, n-amyl alcohol and 2- hexanol or
A variety of combinations.
Preferably, the silane coupling agent additional amount is 2.0 ~ 8.0%(mass percent), the silane coupling agent is ammonia
Propyl trimethoxy silicane, isobutyl ethyl triethoxy silicane, methacryloxypropyl silane, preferably aminopropyl trimethoxy silicon
Alkane.
A2, nano-silicon/carbon nanotube compound precursor liquid solution preparation:
Carbon nanotube is added in above-mentioned nano-silicon solution and is mixed, the carbon nanotube and the mixing mass ratio of nano-silicon solution are
1:5 ~ 1:20 is dispersed using dispersion machine, and dispersion frequency is 20 ~ 50Hz, and nano-silicon/carbon nanotube composite precursor is obtained after processing
Solution.
A3, soft carbon/nano-silicon/carbon nanotube composite precursor particle preparation:
Soft carbon powder is added in above-mentioned nano-silicon/carbon nanotube compound precursor liquid solution, wherein the soft carbon powder and nanometer
Silicon/carbon nanotube compound precursor liquid solution mass ratio is 1:1-10:1, is stirred dispersion using double planetary mixer, is revolved
Speed is 20-300r/min, rotational velocity 1000-2500r/min, mixing time 2-10h, will stir evenly mixed liquor into
Row spray drying granulation obtains soft carbon/nano-silicon/carbon nanotube precursor, and soft carbon/nano-silicon/carbon nanotube precursor granularity is
20-30μm。
A4, building clad:
Use carbon source material as covering material, is carried out using mechanical solid phase cladding, liquid phase coating or gas phase method for coating complete
Surface cladding.
Solid phase cladding, liquid phase coating or gas phase cladding are the prior arts, and solid phase cladding refers to: presoma is equal with asphalt mixing
It is even, under nitrogen protection, carbonization cladding is carried out in batch-type furnace, roller kilns, pushed bat kiln；Liquid phase coating refers to: by pitch with molten
Agent dissolution, is stirred cladding, nitrogen protection with presoma in the equipment with shearing force such as rotary drum furnace；Gas phase cladding refers to:
Organic carbon source (PVA, PAN, glucose) gasification is passed through CVD furnace, is coated under nitrogen protection in fluidized bed；
Preferably, the carbon source material is in hydro carbons, alkanes, alkenes, phenols, carbohydrate, organic acid, resinae and high molecular material
Any a kind or at least two kinds of of combination, preferably methane, ethylene, pitch, phenolic resin, epoxy resin, polyvinyl alcohol, polychlorostyrene
Ethylene, polyethylene glycol, sucrose, glucose, a kind or at least two kinds of of combination in polyacrylonitrile.Cladding ratio is 1:100-1:
10, sintering temperature is 700 ~ 1000 DEG C, and the thermal reduction time is 10 ~ 240min, and thermal reduction heating rate is 0.5 ~ 15.0 DEG C/min.
The protective gas that cladding process uses is helium, nitrogen, any a kind or at least two kinds of of combination in argon gas；Reactor is true
Empty furnace, rotary furnace, batch-type furnace, pushed bat kiln or tube furnace.
Compared with prior art, the present invention is had the advantages that
1, two kinds of soft carbon, silicon negative electrode materials by being effectively combined together by the present invention by structure building, the composite material
The high power density of soft carbon and the high-energy density of silicon are combined, newly establishing one kind not only has high-energy density but also have high power
The composite material of density, the material had both had the high-energy density of silicon, and this composite wood in the high power density for having both soft carbon
Material has synergistic effect, can effectively make up the low tapped density of soft carbon and the circulation expansion issues of silicon.
2, nano-silicon is dispersed in carbon nanotube, can effectively improves the electric conductivity of nano-silicon, and inhibit
The expansion of nano-silicon advantageously forms the conductive network to extend in all direction in the composite.
3, by uniformly preparing one layer of conductive carbon layer on soft carbon/silicon/carbon nanotube precursor surface, so that it is with lower
Specific surface area, improve cyclical stability, and the processing performance of powder can be effectively improved.
Detailed description of the invention
Fig. 1 is the schematic diagram of nano silicon composite cathode material prepared by embodiment 1.
Fig. 2 is the scanning electron microscope SEM figure of nano silicon composite cathode material prepared by embodiment 1.
Fig. 3 is the XRD diagram of nano silicon composite cathode material prepared by embodiment 1.
In attached drawing: 1-nano-silicon, 2-soft carbons, 3-carbon nanotubes, 4-clads.
Specific embodiment
With reference to the accompanying drawing and specific embodiment the present invention will be further described.
Embodiment 1
(1) it is receiving for 100nm that silane coupling agent aminopropyl trimethoxysilane is added to the middle partial size being scattered in alcohol solvent
It is mixed in rice silicon powder flask, mixed proportion 1:5, is subsequently placed into progress ultrasound 2h in ultrasonic cleaner, supersonic frequency is adjusted
For 30kHZ, the nano-silicon solution being dispersed in ethanol system is finally obtained；
(2) carbon nanotube (caliber 5nm, length 100nm) is added in above-mentioned nano-silicon solution and is mixed, mixed proportion 1:5 makes
With dispersion machine high speed dispersion, dispersion frequency 40HZ obtains nano-silicon/carbon nanotube composite particles solution after processing.
(3) the soft carbon powder that partial size is 4 μm is added in above-mentioned nano-silicon/carbon nanotube compound precursor liquid solution, addition
Ratio 1:1 is stirred dispersion, revolution speed 20r/min using double planetary mixer, and rotational velocity 1000r/min is stirred
Mixing the time is 5h, will stir evenly mixed liquor progress spray drying granulation and obtains soft carbon/nano-silicon/carbon nanotube precursor, soft
Carbon/nano-silicon/carbon nanotube precursor granularity is 20 μm.
(4) cladding uses carbon source material for pitch using mechanical solid phase cladding, and cladding ratio is 1:10.The burning
Junction temperature is 600 DEG C, and the thermal reduction time is 10min.The thermal reduction heating rate is 0.5 DEG C/min.The protective gas
For nitrogen；The reactor is batch-type furnace.Obtain nano silicon composite cathode material, the structure of the nano silicon composite cathode material
Schematic diagram is as shown in Figure 1, the scanning electron microscope SEM of the nano silicon composite cathode material schemes as shown in Fig. 2, the nanometer
The XRD diagram of silicon composite cathode material is as shown in Figure 3.
Embodiment 2
(1) silane coupling agent isobutyl ethyl triethoxy silicane is added to the nano-silicon that the middle partial size being scattered in alcohol solvent is 10nm
It is mixed in powder flask, mixed proportion 1:20, is subsequently placed into progress ultrasound 5h, supersonic frequency in ultrasonic cleaner and is adjusted to
50kHZ finally obtains the nano-silicon solution being dispersed in glycol system；
(2) carbon nanotube (caliber 50nm, length 500nm) is added in above-mentioned nano-silicon solution and is mixed, mixed proportion 1:10,
Using dispersion machine high speed dispersion, dispersion frequency 50HZ obtains nano-silicon/carbon nanotube composite particles solution after processing.
(3) it is that 9 μm of soft carbon powder are added in above-mentioned nano-silicon/carbon nanotube compound precursor liquid solution by partial size, adds ratio
Example 2:1 is stirred dispersion, revolution speed 50r/min, rotational velocity 1500r/min, stirring using double planetary mixer
Time is 5h, will stir evenly mixed liquor and carries out spray drying granulation and obtains soft carbon/nano-silicon/carbon nanotube precursor, soft carbon/
Nano-silicon/carbon nanotube precursor granularity is 24 μm.
(4) cladding uses liquid phase coating, uses carbon source material for methane, and cladding ratio is 1:20.The sintering temperature
Degree is 900 DEG C, and the thermal reduction time is 100min.The thermal reduction heating rate is 5 DEG C/min.The protective gas is helium
Gas；The reactor is vacuum drying oven.
Embodiment 3
(1) silane coupling agent methacryloxypropyl silane is added to the nanometer that the middle partial size being scattered in alcohol solvent is 80nm
It is mixed in silicon powder flask, mixed proportion 1:30, is subsequently placed into progress ultrasound 8h, supersonic frequency in ultrasonic cleaner and is adjusted to
80kHZ finally obtains the nano-silicon solution being dispersed in propyl alcohol system；
(2) carbon nanotube (caliber 15nm, 2 μm of length) is added in above-mentioned nano-silicon solution and is mixed, mixed proportion 1:20 makes
With dispersion machine high speed dispersion, dispersion frequency 30HZ obtains nano-silicon/carbon nanotube composite particles solution after processing.
(3) it is that 6 μm of soft carbon powder are added in above-mentioned nano-silicon/carbon nanotube compound precursor liquid solution by partial size, adds ratio
Example 3:1, is stirred dispersion, revolution speed 100r/min using double planetary mixer, rotational velocity 2000r/min is stirred
Mixing the time is 7h, will stir evenly mixed liquor progress spray drying granulation and obtains soft carbon/nano-silicon/carbon nanotube precursor, soft
Carbon/nano-silicon/carbon nanotube precursor granularity is 27 μm.
(4) cladding is coated using gas phase, uses carbon source material for phenolic resin, and cladding ratio is 1:70.The burning
Junction temperature is 700 DEG C, and the thermal reduction time is 180min.The thermal reduction heating rate is 10 DEG C/min.The protective gas
For nitrogen；The reactor is pushed bat kiln.
Embodiment 4
(1) silane coupling agent aminopropyl trimethoxysilane is added to the nanometer that the middle partial size being scattered in alcohol solvent is 50nm
It is mixed in silicon powder flask, mixed proportion 1:50, is subsequently placed into progress ultrasound 10h in ultrasonic cleaner, supersonic frequency is adjusted
For 120kHZ, the nano-silicon solution being dispersed in alcohol system system is finally obtained；
(2) carbon nanotube (caliber 30nm, 5 μm of length) is added in above-mentioned nano-silicon solution and is mixed, mixed proportion 1:15 makes
With dispersion machine high speed dispersion, dispersion frequency 20HZ obtains nano-silicon/carbon nanotube composite particles solution after processing.
(3) it is that 7 μm of soft carbon powder are added in above-mentioned nano-silicon/carbon nanotube compound precursor liquid solution by partial size, adds ratio
Example 10:1, is stirred dispersion, revolution speed 300r/min using double planetary mixer, rotational velocity 2500r/min is stirred
Mixing the time is 10h, will stir evenly mixed liquor progress spray drying granulation and obtains soft carbon/nano-silicon/carbon nanotube precursor, soft
Carbon/nano-silicon/carbon nanotube precursor granularity is 20 μm.
(4) cladding uses carbon source material for pitch using mechanical solid phase cladding, and cladding ratio is 1:100.The burning
Junction temperature is 1000 DEG C, and the thermal reduction time is 240min.The thermal reduction heating rate is 15 DEG C/min.The protective gas
For argon gas；The reactor is rotary furnace.
Comparative example 1:
(1) it is receiving for 100nm that silane coupling agent aminopropyl trimethoxysilane is added to the middle partial size being scattered in alcohol solvent
It is mixed in rice silicon powder flask, mixed proportion 1:5, is subsequently placed into progress ultrasound 2h in ultrasonic cleaner, supersonic frequency is adjusted
For 30kHZ, the nano-silicon solution being dispersed in ethanol system is finally obtained；
(2) carbon nanotube (caliber 5nm, length 100nm) is added in above-mentioned nano-silicon solution and is mixed, mixed proportion 1:5 makes
With dispersion machine high speed dispersion, dispersion frequency 40HZ obtains nano-silicon/carbon nanotube composite particles solution after processing.
(3) above-mentioned uniform mixed liquor is subjected to spray drying granulation and obtains soft carbon/nano-silicon/carbon nanotube precursor, received
Rice silicon/carbon nanotube precursor granularity is 15 μm.
(4) cladding uses carbon source material for pitch using mechanical solid phase cladding, and cladding ratio is 1:10.The burning
Junction temperature is 900 DEG C, and the thermal reduction time is 100min.The thermal reduction heating rate is 5 DEG C/min.The protective gas is
Nitrogen；The reactor is batch-type furnace.
Comparative example 2:
(1) it disperses carbon nanotube (caliber 5nm, length 100nm) in alcohol solvent, uses dispersion machine high speed dispersion, dispersion
Frequency is 40HZ, and nano-silicon/carbon nanotube composite particles solution is obtained after processing.
It (2) is that 4 μm of soft carbon powder are added in above-mentioned carbon nano-tube solution by partial size, adding proportion 1:1 is stirred using double-planet
The machine of mixing is stirred dispersion, revolution speed 20r/min, rotational velocity 1000r/min, and mixing time 2h will be stirred
Even mixed liquor carries out spray drying granulation and obtains soft carbon/carbon nanotube precursor, and soft carbon/carbon nanotube precursor granularity is 17 μ
m。
(3) cladding uses carbon source material for pitch using mechanical solid phase cladding, and cladding ratio is 1:10.The burning
Junction temperature is 600 DEG C, and the thermal reduction time is 10min.The thermal reduction heating rate is 0.5 DEG C/min.The protective gas
For nitrogen；The reactor is batch-type furnace.
Performance test
The negative electrode material that embodiment and comparative example provide is prepared into battery, specific steps are as follows:
In a solvent by negative electrode material, conductive agent and binder 94:2:4 mixed dissolution in mass ratio, control solid content is 50%,
Coated in copper foil current collector, the LiPF6/EC+DMC+EMC (v/v=1:1:1) of cathode pole piece, 1mol/L is made in vacuum drying
Electrolyte, SK diaphragm, lithium piece, shell use the button cell of conventional production process assembly；In Shenzhen Xin Wei Co., Ltd battery
In test macro, test condition are as follows: under room temperature, 0.1C constant current charge-discharge, charge and discharge blanking voltage 0.01V-1.5V.Test result
It is shown in Table 1:
Claims (10)
1. a kind of lithium ion battery high-energy density and high power density negative electrode material, it is characterised in that: the high-energy is close
Degree is " Kiwi berry " structure with high power density negative electrode material, and " Kiwi berry " structure includes " Kiwi berry " core, " Kiwi berry "
Seed, " Kiwi berry " pulp and " Kiwi berry " crust, " Kiwi berry " core are soft carbon matrix, and " Kiwi berry " seed is uniformly to divide
It is dispersed in the nano silicon material of soft carbon matrix surface, " Kiwi berry " pulp is to be dispersed in soft carbon matrix and nanometer silicon face
Carbon nanotube, " Kiwi berry " crust is conductive carbon coating layer.
2. a kind of lithium ion battery high-energy density according to claim 1 and high power density negative electrode material, special
Sign is: the soft carbon matrix is 2500 DEG C or more graphitisable amorphous carbon materials, and partial size is 4-9 μm；The soft carbon base
Body is a kind or at least two kinds of of combination in petroleum coke, needle coke, carbon fiber and non-graphitized carbonaceous mesophase spherules.
3. a kind of lithium ion battery high-energy density according to claim 1 and high power density negative electrode material, special
Sign is: the nano silicon material is polysilicon, monocrystalline silicon, amorphous silicon；Preferably, the nano silicon material is monodispersed list
Crystal silicon or polycrysalline silcon；Preferably, the middle partial size of the nano silicon material is 10 ~ 100nm.
4. a kind of lithium ion battery high-energy density according to claim 1 and high power density negative electrode material, special
Sign is: the carbon nanotube be single wall or multi wall, caliber 5-50nm, 100nm-5 μm of length.
5. a kind of lithium ion battery high-energy density according to claim 1 and high power density negative electrode material, special
Sign is: the conduction carbon coating layer is cracking carbon material；Preferably, the cracking carbon material is organic cracking carbon, preferably
For a kind or at least two kinds of of combination in pitch, carbohydrate and high molecular material, further preferably pitch, phenolic resin, epoxy
Resin, polyvinyl alcohol, polyethylene glycol, polyacrylonitrile, a kind in polyethylene oxide or at least two combination.
6. a kind of preparation method of lithium ion battery high-energy density and high power density negative electrode material, comprising the following steps:
A1, nano-silicon surface modification: silane coupling agent being added in the flask of alcohol system nano-silicon slurries and mixed, the silane
The mixing mass ratio of coupling agent and alcohol system nano-silicon slurries is 1:5 ~ 1:50, is then placed in progress ultrasound 2- in ultrasonic cleaner
10h finally obtains the nano-silicon solution being dispersed in alcohol system system；
A2, nano-silicon/carbon nanotube compound precursor liquid solution preparation: carbon nanotube being added in above-mentioned nano-silicon solution and is mixed,
The carbon nanotube and the mixing mass ratio of nano-silicon solution are 1:5 ~ 1:20, are dispersed using dispersion machine, are obtained after decentralized processing
Nano-silicon/carbon nanotube compound precursor liquid solution；
A3, soft carbon/nano-silicon/carbon nanotube composite precursor particle preparation: above-mentioned nano-silicon/carbon nanometer is added in soft carbon powder
In pipe compound precursor liquid solution, wherein the soft carbon powder is with nano-silicon/carbon nanotube compound precursor liquid solution mass ratio
1:1-10:1 is stirred dispersion using double planetary mixer, will stir evenly mixed liquor carry out spray drying granulation obtain it is soft
Carbon/nano-silicon/carbon nanotube composite precursor particle；
A4, building clad: use carbon source material as covering material, using mechanical solid phase cladding, liquid phase coating or gas phase packet
Coating method carries out full surface cladding to soft carbon/nano-silicon/carbon nanotube composite precursor particle.
7. the preparation of a kind of lithium ion battery high-energy density and high power density negative electrode material according to claim 1
Method, it is characterised in that: in step A1, the alcohol system medium in the alcohol system nano-silicon slurries is methanol, ethyl alcohol, ethylene glycol, third
Alcohol, isopropanol, 1,2- propylene glycol, glycerine, n-butanol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, n-amyl alcohol and
The combination of one or more in 2- hexanol.
8. the preparation of a kind of lithium ion battery high-energy density and high power density negative electrode material according to claim 1
Method, it is characterised in that: in step A1, the silane coupling agent be aminopropyl trimethoxysilane, isobutyl ethyl triethoxy silicane,
Methacryloxypropyl silane, preferably aminopropyl trimethoxysilane.
9. the preparation of a kind of lithium ion battery high-energy density and high power density negative electrode material according to claim 1
Method, it is characterised in that: in step A4, the carbon source material is hydro carbons, alkanes, alkenes, phenols, carbohydrate, organic acid, resinae
With any a kind or at least two kinds of of combination in high molecular material, preferably methane, ethylene, pitch, phenolic resin, asphalt mixtures modified by epoxy resin
Rouge, polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, sucrose, glucose, a kind or at least two kinds of of combination in polyacrylonitrile.
10. the system of a kind of lithium ion battery high-energy density and high power density negative electrode material according to claim 1
Preparation Method, it is characterised in that: in step A4, cladding ratio is 1:100-1:10, and sintering temperature is 700 ~ 1000 DEG C, when thermal reduction
Between be 10 ~ 240min, thermal reduction heating rate be 0.5 ~ 15.0 DEG C/min, cladding process use protective gas, the protection
Property gas be helium, nitrogen, a kind or at least two kinds of of combination in argon gas.
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| CN110635128A (en) * | 2019-09-26 | 2019-12-31 | 湖南中科星城石墨有限公司 | Negative electrode composite material for lithium ion battery and preparation method thereof |
| CN111180713A (en) * | 2020-02-10 | 2020-05-19 | 马鞍山科达普锐能源科技有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN111554898A (en) * | 2020-05-11 | 2020-08-18 | 珠海冠宇电池股份有限公司 | Negative electrode material and preparation method and application thereof |
| CN111755680A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
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| CN114665083A (en) * | 2022-03-21 | 2022-06-24 | 深圳市贝特瑞新能源技术研究院有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
| CN114665083B (en) * | 2022-03-21 | 2024-07-02 | 深圳市贝特瑞新能源技术研究院有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
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