CN110504430A - A kind of lithium ion battery silicon-carbon cathode material and preparation method thereof - Google Patents
A kind of lithium ion battery silicon-carbon cathode material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of lithium ion battery silicon-carbon cathode material and preparation method thereof, include: S1, carries out wet grinding under oxidative conditions after silicon source and solvent are mixed, silicon source surface is made to form oxide layer, oxygen element quality accounts for the 9.8%-14% of silicon source quality, obtains slurry；S2, slurry obtained by step S1 and carbon material progress is compound, it is dry, obtain silicon-carbon inner nuclear material；Silicon-carbon inner nuclear material obtained by step S2 is carried out fusion process, then is uniformly mixed with carbon encapsulated material by S3, high-temperature calcination molding；Step S3 resulting material is crushed by S4, and screening obtains silicon-carbon cathode material.The present invention is during wet grinding, realize the controllable oxidization to nano-silicon, silicon source surface is set to form oxide layer, the presence of oxide layer reduces electrochemistry agglomeration in cyclic process while avoiding silicon source and electrolyte side reaction, and then is added significantly to the cyclical stability of silicon-carbon cathode material.
Description
Technical field
The present invention relates to technical field of chemical power more particularly to a kind of lithium ion battery silicon-carbon cathode material and its preparations
Method.
Background technique
New type lithium ion secondary cell is one of the hot spot of new energy field development, because specific energy is high, operating voltage is high,
The unique advantages such as temperature limit is wide, has extended cycle life, is pollution-free and receive much attention, be to be answered in current commercialization secondary cell
With most commonly used system, immense success is achieved in field of portable electronic apparatus, and application range is still constantly being opened up
One of width, and have become the most important electrical source of power of new-energy automobile.
Industrialization lithium-ion-power cell is primarily present the problems such as energy density is low, at high cost, and solves these problems
Key be then electrode material performance promotion.Four big raw material one of of the negative electrode material as lithium battery, are no more than in capacity
In the case where 1200mAh/g, improving its existing capacity still has very big contribution to the promotion of entire battery energy density, together
When very important effect is played to the especially safety of lithium battery performance.Current commercialized lithium ion battery mostly uses graphite
Class charcoal cathode, but its lower specific capacity (theoretical capacity 372mAh/g), high rate performance and safety problem that may be present are
It is not able to satisfy the actual needs of high-performance power battery.Silicon is with the gram volume (4200mAh/g) of its superelevation, environmental-friendly, storage
The advantages that amount is abundant is considered as the negative electrode material of next-generation lithium ion battery with high energy density, but there are huge when its charge and discharge
Volume change causes the serious metamorphosis of material, and then influences the cycle performance of electrode material, causes cycle performance bad.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of lithium ion battery silicon-carbon cathode material and its preparation
The cycle performance of method, gained lithium ion battery silicon-carbon cathode material improves.
The present invention is to be achieved through the following technical solutions:
A kind of preparation method of lithium ion battery silicon-carbon cathode material, includes the following steps:
S1 carries out wet grinding after mixing silicon source and solvent under oxidative conditions, silicon source surface is made to form oxide layer, oxygen
Element quality accounts for the 9.8%-14% of silicon source quality, obtains slurry；
S2, slurry obtained by step S1 and carbon material progress is compound, it is dry, obtain silicon-carbon inner nuclear material；
Silicon-carbon inner nuclear material obtained by step S2 is carried out fusion process, then is uniformly mixed with carbon encapsulated material by S3, high
Temperature calcining molding；
Step S3 resulting material is crushed by S4, and screening obtains silicon-carbon cathode material.
Preferably, in step S1, oxidizing condition specifically: be passed through air, or the mixture of water and ethyl alcohol is added.
Preferably, in step S1, silicon source is one of polysilicon, monocrystalline silicon, metallic silicon, silicon alloy and Si oxide；
Solvent is one of water, ethyl alcohol, N-Methyl pyrrolidone, acetone and ethylene glycol.
Preferably, in step S1, it is additionally added dispersing agent, mixes dispersing agent with silicon source and solvent；Dispersing agent is lignin
One of sulphonic acids, polyethylene glycol, seaweed acids, polyacrylic, polyvinylpyrrolidone, stearic acid and sodium humate.
Preferably, in step S2, with carbon material carry out it is compound before, conductive agent also is added into slurry obtained by step S1, then
Wet grinding；Conductive agent is graphene and/or carbon nanotube.
Preferably, in step S2, carbon material is one of graphite, nanofiber and porous carbon.
Preferably, in step S2, drying mode is one of dry distillation, spray drying and freeze-drying.
Preferably, in step S3, calcination temperature is 200~1000 DEG C, and calcination time is 3~12h.
Preferably, in step S3, carbon encapsulated material is pitch, resin, citric acid, sucrose, glucose, polyvinylpyrrolidine
Any one of ketone, starch, dextrin, polyaniline and polyimides.
The lithium ion battery silicon-carbon cathode material that the preparation method is prepared.
Compared with prior art, the invention has the following beneficial technical effects:
The preparation method of lithium ion battery silicon-carbon cathode material of the present invention is realized during wet grinding to nanometer
The controllable oxidization of silicon makes silicon source surface form oxide layer, and the presence of oxide layer is while avoiding silicon source and electrolyte side reaction
Reduce electrochemistry agglomeration in cyclic process, and then is added significantly to the cyclical stability of silicon-carbon cathode material.Meanwhile this
Invention combines oxidation process with the broken of silicon source, dispersing technology, avoids the introducing of independent oxidation technology, reduces preparation
Processing step.Nano-silicon is compound with carbon material, carries out carbon coating, forms core-shell structure, reserves expansion space for silicon source, avoids
Dusting of the material in cyclic process, and contribute to form stable electrolyte solid electrolyte interface film.The present invention passes through wet
Powerful impact force and fluid velocity is generated in method process of lapping silicon source is crushed to Nano grade and is uniformly dispersed in solvent
In, effect is easy to batchprocess amplification better than technologies such as stirring, ultrasounds.The present invention is by easy-to-use method to nanometer
Silicon is surface modified, and is prepared for the silicon-carbon cathode material with core-shell structure, in basic guarantee specific capacity and first charge discharge efficiency
While, cycle performance is substantially increased, simple process, production cost are low, are suitable for industrialized production.
Further, oxidizing condition of the invention selection is passed through air, or the mixture of water and ethyl alcohol is added, and is grinding
Oxidation reaction occurs with newly-generated silicon face in the process, it is not only at low cost, and also oxidation is weak, and it can be to avoid other oxidants
Excessive oxidation and caused by adverse effect.
Further, dispersing agent is added, can further promote the dispersion of nano-silicon.
Further, conductive agent graphene and/or carbon nanotube is added, plays the role of improving material conductivity.
Further, the present invention selects suitable drying mode to realize that silicon source is distributed in the mixing of carbon material surface, avoids
Because slurry drying time too long nano-silicon it is heated it is mobile, reunite the problem of, this is to the volume expansion problem for alleviating silicon carbon material
It is significant.
Lithium ion battery silicon-carbon material prepared by preparation method of the present invention, specific capacity and first charge discharge efficiency are high, have extended cycle life.
Detailed description of the invention
Fig. 1 is the silicon carbon material sem test result in the embodiment of the present invention 1；
Fig. 2 is the silicon carbon material sem test result in the embodiment of the present invention 2.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
The present invention provides a kind of lithium ion battery silicon/carbon negative pole material and preparation method thereof, passes through easy-to-use method
Nano-silicon is surface modified, the silicon-carbon cathode material with core-shell structure is prepared for.It is imitated with height ratio capacity and for the first time
While rate, take into account excellent cycle performance, simple process, production cost be low, it is energy-saving, be suitable for industrialized production.
The present invention provides a kind of lithium ion battery silicon-carbon cathode material, with core-shell structure, the quality percentage of element silicon
Number is 3~50%, and the mass percent of carbon is 50~97%, also contains a small amount of oxygen element, the partial size of silicon source is 5~
250nm, the partial size of the graphite material of addition are 0.1~40um.Wherein it is preferred to which the partial size of silicon source is 40~100nm；It is added
Graphite partial size be 5~15um.
The preparation method of high performance silicon/carbon negative pole material of the present invention, the specific steps are as follows:
S1: wet grinding 2-6h is carried out under oxidative conditions after silicon source, dispersing agent and solvent are mixed, makes silicon source surface shape
At oxide layer, oxygen element quality accounts for the 9.8%-14% of silicon source quality, to obtain evenly dispersed nano-silicon slurry in a solvent；
The solid content of silicon in a solvent is 1~50%；Silicon source is polysilicon, monocrystalline silicon, metallic silicon, silicon alloy and silicon oxidation
The combination of one or more of object；Dispersing agent is sulfomethylated lignin acids, polyethylene glycol, seaweed acids, polyacrylic, poly- second
One of alkene pyrrolidone, stearic acid and sodium humate or a variety of combinations；Solvent is deionized water, ethyl alcohol, N- methyl pyrrole
The combination of one or more of pyrrolidone, acetone and ethylene glycol.Oxidizing condition specifically: be passed through air, or be added water and
The mixture of ethyl alcohol.
S2: slurry and carbon material ground in step S1 are subjected to compound rear drying, it is made to be uniformly dispersed in carbon materials
Expect surface, obtains silicon-carbon inner nuclear material；
Carbon material is the combination of one or more of graphite, nanofiber and porous carbon, drying mode be distillation it is dry,
One of spray drying and freeze-drying.
S3: it after silicon-carbon inner nuclear material obtained in S2 is carried out fusion process, then mixes with carbon encapsulated material, high temperature
Calcining molding；
Carbon encapsulated material is pitch, resin, citric acid, sucrose, glucose, polyvinylpyrrolidone, starch, dextrin, gathers
The combination of any one or more of aniline, pitch and polyimides, calcination temperature be 200~1000 DEG C, calcination time be 3~
12h。
S4: taking step S3 material to be crushed, and screening obtains the silicon-carbon cathode material with core-shell structure, D50 partial size
For 5~40um.
In S2, with carbon material carry out it is compound before, conductive agent is added in ground nano-silicon slurry also into step S1, then
Wet grinding obtains slurry；Conductive agent is graphene and/or carbon nanotube.
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
Technical solution of the present invention is clearly and completely described, it is clear that described embodiment is that a part of the invention is implemented
Example, instead of all the embodiments.The component of the embodiment of the present invention usually described herein with shown in can be by various
Different configurations is arranged and is designed.Therefore, the detailed description of embodiment of the invention below is not intended to limit claimed
The scope of the present invention, but be merely representative of selected embodiment of the invention.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
The preparation of high performance silicon/carbon negative pole material
(1) 1440g ethyl alcohol is added in sand mill tank, 160g polycrystalline micron silicon is added and stirs 15min, it is stearic that 1.6g is added
Acid is passed through air in agitator tank, starts grinder, grinds 4h, rear that 16g graphene, 8g carbon nanotube, then wet grinding is added
2h；Part size is taken to be dried in vacuo, oxygen-nitrogen analyzer measures the oxygen content of nano-silicon, and test result is shown in Table 1；
(2) 30min is mixed in the slurry and 92g fine powder graphite for taking step 1 to obtain；
(3) it takes slurries in step 2 to be spray-dried, obtains silicon-carbon inner nuclear material；
(4) after merging presoma in step 3 in horizontal fusion machine, pitch is added and is coated, under nitrogen protection
High-temperature calcination carbonization；Calcination temperature is 1000 DEG C, calcination time 3h；
(5) it takes step 4 material to be crushed, sieves, obtain the silicon-carbon cathode material with core-shell structure, D50 partial size
It is 15.7 microns.
The physico-chemical property of Si-C composite material characterizes:
The microscopic appearance of the silicon carbon material obtained under above-mentioned condition is shown in Fig. 1, it can be seen that material is in preferable spherical structure,
Surface indentation, nano-silicon are closely combined with each other with carbon material, form the composite material of core-shell structure with multicore.
Silicon-carbon cathode material, conductive agent (Super P) and adhesive (PVDF) ratio of 80:10:10 in mass ratio are filled
Divide and be ground into slurry, then the electrode material after mixing is coated on copper foil, pole piece is made.Pole piece is at 60 DEG C in vacuum drying
It is spare to be cut to the disk that diameter is 1.6cm for drying in case after 12 hours.To cut the pole piece of size for anode, with lithium metal
Piece does cathode, is assembled into CR2032 type button cell.Charge and discharge blanking voltage is respectively 2.0V and 0.01V, and test result is shown in Table 2
In.
Embodiment 2
(1) 1440g ethyl alcohol is added in sand mill tank, 160g monocrystalline micron silicon is added and stirs 15min, leads in agitator tank
Enter air, start grinder, grind 6h, part size is taken to be dried in vacuo, oxygen-nitrogen analyzer measures the oxygen content of nano-silicon, test
It the results are shown in Table 1；
(2) take slurry and 1400g graphite in step 1 that 30min is mixed；
(3) it takes slurries in step 2 to be spray-dried, obtains silicon-carbon inner nuclear material；
(4) after merging presoma in step 3 in horizontal fusion machine, pitch is added and is coated, under nitrogen protection
High-temperature calcination carbonization；Calcination temperature is 800 DEG C, calcination time 5h；
(5) it takes step 4 material to be crushed, sieves, obtain the silicon-carbon cathode material with core-shell structure, D50 partial size
It is 15.5 microns.
The physico-chemical property of Si-C composite material characterizes:
The microscopic appearance of the silicon carbon material obtained under above-mentioned condition is shown in Fig. 2, it can be seen that material is in preferable spherical structure,
Nano-silicon is closely combined with each other with carbon material.Electrochemical test method is same as Example 1, and test result is shown in Table in 2.
Embodiment 3
(1) 1440g ethyl alcohol and 10g water are added in sand mill tank, 160g nano-metal silicon is added and stirs 15min, is added
200g PVP is passed through nitrogen in agitator tank, starts grinder, grinds 2h, rear that 16g graphene, 8g carbon nanotube, rewetting is added
Method grinds 2h, and part size is taken to be dried in vacuo, and oxygen-nitrogen analyzer measures the oxygen content of nano-silicon, and test result is shown in Table 1；
(2) take slurry and 1400g graphite in step 1 that 30min is mixed；
(3) it takes slurries in step 2 to be spray-dried, obtains silicon-carbon inner nuclear material；
(4) after merging presoma in step 3 in horizontal fusion machine, pitch is added and is coated, under nitrogen protection
High-temperature calcination carbonization；Calcination temperature is 200 DEG C, calcination time 10h；
(5) it takes step 4 material to be crushed, sieves, obtain the silicon-carbon cathode material with core-shell structure.
Electrochemical test method embodiment 1 is identical, and test result is shown in Table in 2.
Embodiment 4
(1) 1440g ethyl alcohol and 10g water are added in high speed ball mill tank, 100 nanometers of monocrystalline silicon powder 160g is added, opens
Dynamic ball mill, grinds 2h；Part size is taken to be dried in vacuo, oxygen-nitrogen analyzer measures the oxygen content of nano-silicon, and test result is shown in Table
1；
(2) take slurry and 1400g graphite in step 1 that 30min is mixed；
(3) it takes slurries in step 2 to be spray-dried, obtains silicon-carbon inner nuclear material；
(4) after merging presoma in step 3 in horizontal fusion machine, resin is added and is coated, under nitrogen protection
High-temperature calcination carbonization；Calcination temperature is 500 DEG C, calcination time 12h；
(5) it takes step 4 material to be crushed, sieves, obtain the silicon-carbon cathode material with core-shell structure, D50 partial size
It is 15.5 microns.
Electrochemical test method embodiment 1 is identical, and test result is shown in Table in 2.
Embodiment 5
(1) 1440g acetone is added in high speed ball mill tank, 160g monocrystalline silicon powder is added, polyethylene glycol is added, starts ball
Grinding machine grinds 2h；
(2) take slurry and 1400g porous carbon in step 1 that 30min is mixed；
(3) slurry freeze drying in step 2 is taken, silicon-carbon inner nuclear material is obtained；
(4) after merging presoma in step 3 in horizontal fusion machine, polyvinylpyrrolidone is added and is coated, In
High-temperature calcination is carbonized under nitrogen protection；Calcination temperature is 700 DEG C, calcination time 8h；
(5) it takes step 4 material to be crushed, sieves, obtain the silicon-carbon cathode material with core-shell structure.
Embodiment 6
(1) 1440g N-Methyl pyrrolidone is added in high speed ball mill tank, 160g metallic silicon power is added, seaweed is added
Acid starts ball mill, grinds 2h；16g graphene, then wet grinding 2h are added afterwards；
(2) take slurry and 1400g carbon fiber in step 1 that 30min is mixed；
(3) it takes slurries in step 2 to be spray-dried, obtains silicon-carbon inner nuclear material；
(4) after merging presoma in step 3 in horizontal fusion machine, polyaniline is added and is coated, in nitrogen protection
Lower high-temperature calcination carbonization；Calcination temperature is 500 DEG C, calcination time 10h；
(5) it takes step 4 material to be crushed, sieves, obtain the silicon-carbon cathode material with core-shell structure.
Comparative example 1
(1) 1440g ethyl alcohol is added in sand mill tank, polycrystalline micron silicon 160g is added and stirs 15min, leads in agitator tank
Enter nitrogen, continue to stir 30min, start grinder, grinds 4h, it is rear that 16g graphene, 8g carbon nanotube, then wet grinding is added
2h；Slurry is dried in vacuo, the oxygen content of oxygen-nitrogen analyzer measurement nano-silicon, in test result and table 1；
(2) other steps are same as Example 1, and Electrochemical results are shown in Table in 2.
Comparative example 2
(1) 1440g ethyl alcohol is added in sand mill tank, polycrystalline micron silicon 160g is added and stirs 15min, leads in agitator tank
Enter nitrogen, start grinder, grind 6h, slurry is dried in vacuo, oxygen-nitrogen analyzer measures the oxygen content of nano-silicon, test result
It is shown in Table 1；
(2) other steps are same as Example 2, and electro-chemical test test result is shown in Table in 2.
Oxygen content test result in 1 nano-silicon of table
| Test batch | Milling time | Oxygen content/% |
| Embodiment 1 | 6h | 13.51 |
| Embodiment 2 | 6h | 13.98 |
| Embodiment 3 | 4h | 9.80 |
| Embodiment 4 | 2h | 10.23 |
| Comparative example 1 | 6h | 4.58 |
| Comparative example 2 | 6h | 4.86 |
2 Si-C composite material Electrochemical results of table
As it can be seen from table 1 after grinding under oxidative conditions, obtained Oxygen in silicon content is improved using the method for the present invention.
From table 2 it can be seen that stability is above comparative example when the material of preparation of the embodiment of the present invention is used as electrode material.Embodiment 1
Compare with comparative example 1, although charge specific capacity is in a slight decrease, it is very small to reduce amplitude, but cyclical stability has and substantially mentions
It rises.Embodiment 2 is compared with comparative example 2, and charge specific capacity etc. is substantially suitable, but cyclical stability is substantially improved.It is possible thereby to
Find out, Oxygen in silicon content can be improved using method of the invention, to improve the cyclical stability of material.
Claims (10)
1. a kind of preparation method of lithium ion battery silicon-carbon cathode material, which comprises the steps of:
S1 carries out wet grinding after mixing silicon source and solvent under oxidative conditions, silicon source surface is made to form oxide layer, oxygen element
Quality accounts for the 9.8%-14% of silicon source quality, obtains slurry；
S2, slurry obtained by step S1 and carbon material progress is compound, it is dry, obtain silicon-carbon inner nuclear material；
Silicon-carbon inner nuclear material obtained by step S2 is carried out fusion process, then is uniformly mixed with carbon encapsulated material by S3, and high temperature is forged
Firing type；
Step S3 resulting material is crushed by S4, and screening obtains silicon-carbon cathode material.
2. the preparation method of lithium ion battery silicon-carbon cathode material according to claim 1, which is characterized in that step S1
In, oxidizing condition specifically: be passed through air, or the mixture of water and ethyl alcohol is added.
3. the preparation method of lithium ion battery silicon-carbon cathode material according to claim 1, which is characterized in that step S1
In, silicon source is one of polysilicon, monocrystalline silicon, metallic silicon, silicon alloy and Si oxide；Solvent is water, ethyl alcohol, N- methyl pyrrole
One of pyrrolidone, acetone and ethylene glycol.
4. the preparation method of lithium ion battery silicon-carbon cathode material according to claim 1, which is characterized in that step S1
In, it is additionally added dispersing agent, mixes dispersing agent with silicon source and solvent；Dispersing agent is sulfomethylated lignin acids, polyethylene glycol, alginic acid
One of class, polyacrylic, polyvinylpyrrolidone, stearic acid and sodium humate.
5. the preparation method of lithium ion battery silicon-carbon cathode material according to claim 1, which is characterized in that step S2
In, with carbon material carry out it is compound before, conductive agent, then wet grinding also is added into slurry obtained by step S1；Conductive agent is graphite
Alkene and/or carbon nanotube.
6. the preparation method of lithium ion battery silicon-carbon cathode material according to claim 1, which is characterized in that step S2
In, carbon material is one of graphite, nanofiber and porous carbon.
7. the preparation method of lithium ion battery silicon-carbon cathode material according to claim 1, which is characterized in that step S2
In, drying mode is one of dry distillation, spray drying and freeze-drying.
8. the preparation method of lithium ion battery silicon-carbon cathode material according to claim 1, which is characterized in that step S3
In, calcination temperature is 200~1000 DEG C, and calcination time is 3~12h.
9. the preparation method of lithium ion battery silicon-carbon cathode material according to claim 1, which is characterized in that step S3
In, carbon encapsulated material be pitch, resin, citric acid, sucrose, glucose, polyvinylpyrrolidone, starch, dextrin, polyaniline and
Any one of polyimides.
10. the lithium ion battery silicon-carbon cathode material that the described in any item preparation methods of claim 1-9 are prepared.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111354937A (en) * | 2020-04-21 | 2020-06-30 | 隆能科技(南通)有限公司 | Preparation method of core-shell structure high-capacity silicon-carbon composite negative electrode material for lithium ion battery |
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| CN111354937A (en) * | 2020-04-21 | 2020-06-30 | 隆能科技(南通)有限公司 | Preparation method of core-shell structure high-capacity silicon-carbon composite negative electrode material for lithium ion battery |
| CN111354937B (en) * | 2020-04-21 | 2022-03-11 | 隆能科技(南通)有限公司 | Preparation method of core-shell structure high-capacity silicon-carbon composite negative electrode material for lithium ion battery |
| CN113839014B (en) * | 2020-06-08 | 2023-08-29 | 中国石油化工股份有限公司 | Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery |
| CN113839014A (en) * | 2020-06-08 | 2021-12-24 | 中国石油化工股份有限公司 | Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery |
| CN111668466A (en) * | 2020-06-16 | 2020-09-15 | 清华大学深圳国际研究生院 | Silicon-carbon cathode material with silicon controlled rectifier coating weight and manufacturing method thereof |
| CN111755682A (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 and preparation method thereof |
| CN111755676A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Silicon alloy negative electrode material for lithium ion battery and preparation method thereof |
| CN111755683A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Silicon-containing negative electrode material for lithium ion battery and preparation method thereof |
| CN112687861A (en) * | 2020-12-28 | 2021-04-20 | 华中科技大学 | Silicon oxide and preparation method and application thereof |
| CN112687861B (en) * | 2020-12-28 | 2023-03-10 | 华中科技大学 | Silicon oxide and preparation method and application thereof |
| CN113036306A (en) * | 2021-02-20 | 2021-06-25 | 山东天瀚新能源科技有限公司 | Silicon-doped lithium supplement technical scheme and assembly method of lithium ion battery |
| CN114068891A (en) * | 2021-02-20 | 2022-02-18 | 贝特瑞新材料集团股份有限公司 | Silicon-carbon composite negative electrode material, preparation method thereof and lithium ion battery |
| CN116613299A (en) * | 2023-07-17 | 2023-08-18 | 浙江锂宸新材料科技有限公司 | Preparation method of novel silicon-carbon anode material and product thereof |
| CN116613299B (en) * | 2023-07-17 | 2023-11-24 | 浙江锂宸新材料科技有限公司 | Preparation method of silicon-carbon anode material and product thereof |
| CN116936750A (en) * | 2023-09-18 | 2023-10-24 | 季华实验室 | Lithium ion battery negative electrode plate, preparation method thereof, negative electrode plate slurry and lithium ion battery |
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