CN106684336A - Preparation method for high-combination degree lithium battery carbon silicon anode material - Google Patents
Preparation method for high-combination degree lithium battery carbon silicon anode material Download PDFInfo
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- CN106684336A CN106684336A CN201611211693.4A CN201611211693A CN106684336A CN 106684336 A CN106684336 A CN 106684336A CN 201611211693 A CN201611211693 A CN 201611211693A CN 106684336 A CN106684336 A CN 106684336A
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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
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method for a high-combination degree lithium battery carbon silicon anode material and belongs to the technical field of a lithium ion battery. According to the method, washed rice hulls are dried; after the rice hulls are cooled to the room temperature, ball-milling is carried out on the rice hulls to obtain rice hull powder; the rice hull powder is placed in a vacuum pyrolyzing device; air is eliminated by importing nitrogen; then vacuumization is carried out; a pyrolyzing furnace is heated up and then is cooled, thereby obtaining pyrolyzed rice hull ashes; the rice hull ashes are mixed with hydrochloric acid solution; ultrasonic dispersion and filtering are carried out; filtering cakes are collected; the filtering cakes and sodium hydroxide are stirred and mixed; dispersion liquid is mixed ultrasonically and dispersedly; the dispersion liquid, hydrochloric acid and sodium dodecylbenzene sulfonate are placed in a beaker; centrifugation is carried out after stirring and mixing are carried out; lower layer sediments are collected and are placed in a muffle furnace; the air is eliminated by importing the nitrogen; cooling is carried out after calcining is carried out; and ball-milling is carried out on the calcined mixture, thereby obtaining the high-combination degree lithium battery carbon silicon anode material. The high-combination degree lithium battery carbon silicon anode material prepared by the method has excellent cycling performance and relatively low volume expansion effect. The safety performance is high. The anode material can be popularized.
Description
Technical field
The invention discloses a kind of preparation method of high conjugation lithium battery carbon silicium cathode material, belongs to lithium ion battery
Technical field.
Background technology
With economic fast development, global range Energy situation is increasingly serious, the disposable energy of the tradition such as coal, oil
Demand still persistently increases, while the destruction to global ecological environment is also aggravating.Therefore, to cleaning, low-carbon environment-friendly and can be again
The exploitation of the raw energy becomes the problem that the mankind need joint exploration badly with application.With the development of energy storage technology, wind energy, solar energy
It is greatly improved etc. the application of regenerative resource.At present, hotter energy storage lithium ion battery is studied, in portable electronic
It is widely used in equipment such as notebook and smart mobile phone.But, in order to realize lithium ion battery in environment-protecting clean, nothing
Application on the new-energy automobile of disposal of pollutants, exploitation high-energy, high power density, the lithium-ion electric of new generation of high safety performance
Pond is extremely urgent.
Due to higher lithium storage content and rich in natural resources, silicon materials be considered as exploitation high-energy-density of new generation and
One of ideal candidates material of the lithium ion battery negative material of high power density.However, silicon materials capacity in use
Decay is very fast so as to which practical application is subject to certain restrictions.Think, the volumetric expansion of silicon materials removal lithium embedded shrinks larger, from
And the overall structure of material is destroyed, making the conductivity of material reduces, and this is to cause material capacity decay main faster
Reason.
Then silica flour and graphite mixing and ball milling are added Colophonium or polymer overmold material by patent CN200810031840.9
Material ball milling again, carbonization treatment, after crushed, obtain a kind of lithium ion battery silicon-carbon composite negative pole with shell-core structure
Material, its center is elemental silicon and graphite, and shell is Colophonium or the pyrolytic carbon of polymer overmold material, the material cell energy density
Height, good cycle.But, the difference in hardness of graphite and silicon is larger, and together mixing and ball milling is extremely inefficient, graphite hardness compared with
It is little, for silicon produces resilient protection effect in mechanical milling process, it is difficult to make nano-silicon obtain effective ball milling.
The content of the invention
The technical problem to be solved：Larger for the difference in hardness of graphite and silicon, together mixing and ball milling is imitated
Rate is extremely low, and graphite hardness is less, for silicon produces resilient protection effect in mechanical milling process, it is difficult to make nano-silicon obtain effective ball
The defect of mill.The invention provides one kind will be reacted after rice husk thermal decomposition and pickling with sodium hydroxide, organic matter carbon is dispersed
Into Ludox, simultaneously calcining prepares elemental silicon to subsequent dewatering, organic matter carbon granule is uniformly coated into simple substance silicon crystal, carbon
Grain cannot form resilient protection in its mechanical milling process, so that the method for the effective ball milling of elementary silicon, the present invention first will be clean
Rice husk be dried, be cooled to after room temperature and its ball milling obtained into rice husk powder, in being placed on vacuum pyrolysis device, and logical nitrogen
To exclude air, it is subsequently vacuumed out, cools down after heating up to pyrolysis oven, obtain pyrolysis rice hull ash, then mixes it with hydrochloric acid solution,
In ultrasound wave dispersion, filter, collect filter cake, and mix with sodium hydroxide stirring, the dispersedly mixed dispersion liquid under ultrasound wave, with
Hydrochloric acid, dodecylbenzene sodium sulfonate are placed in beaker, are centrifuged after stirring mixing, are collected lower sediment and are placed in Muffle furnace, are led to
Argon excludes air, cools down after calcining, and calcining mixt is carried out into ball milling, obtains high conjugation lithium battery carbon silicium cathode material.
Conjugation lithium battery carbon silicium cathode material obtained by the present invention has excellent cycle performance and relatively low Volumetric expansion, peace
Full performance is high, can promote the use of.
To solve above-mentioned technical problem, the present invention is using technical scheme as described below：
（1）Discarded rice husk is collected, is cleaned and be dried at being placed in 120~130 DEG C 2~3h, subsequently stood and be cooled to room temperature, will
It is dried rice husk to be placed in ball mill device, 3~5h of ball milling under 250~300r/min, after the completion for the treatment of ball milling, crosses 120 mesh sieves, collects
Obtain rice husk powder；
（2）The rice husk powder of above-mentioned preparation is placed in vacuum pyrolysis device, is led to nitrogen and is excluded air, be subsequently vacuumed out to 3.5
~4.0kPa, by 10 DEG C/min 550~600 DEG C are warming up to pyrolysis oven, after insulation 10~15min of pyrolysis, cool to room with the furnace
Temperature, is prepared into pyrolysis rice hull ash；
（3）In mass ratio 1:5, pyrolysis rice hull ash is mixed with the hydrochloric acid solution of mass fraction 10%, the ultrasound point under 200~300W
After dissipating 10~15min, filter cake, then in mass ratio 1 are filtered and collected:5, filter cake and the stirring of the sodium hydroxide of mass fraction 20% is mixed
25~30min is closed, 10~15min of ultrasonic disperse, is prepared into mixed dispersion liquid under 200~300W；
（4）Count by weight, the mixed dispersion liquid of 45~50 parts of above-mentioned preparations, 10~15 parts of mass fractions 10% are weighed respectively
Hydrochloric acid and 5~8 parts of dodecylbenzene sodium sulfonate are placed in beaker, 25~30min of stirring mixing at 45~50 DEG C；
（5）After the completion of to be mixed, then the centrifugation under 2500~3000r/min, collect lower sediment and be placed in Muffle furnace,
Logical argon excludes air, and 3~5h of calcination processing at 1400~1500 DEG C cools to room temperature with the furnace, collects calcining mixt simultaneously
In being placed in ball grinder, 3~5h of ball milling under 250~300r/min crosses 200 mesh sieves, you can be prepared into a kind of high conjugation lithium electricity
Pond carbon silicium cathode material.
The present invention application process be：By the high conjugation lithium battery carbon silicium cathode material obtained by the present invention and conductive agent second
Acetylene black, binding agent PVDF are with 6:1:1~8:1:1 uniform quality mixing, in the environment of ambient humidity is for 10~15%, with N-
Methyl pyrrolidone is applied on Copper Foil for solvent and dries under heat lamp, be subsequently transferred in 120 DEG C of baking oven drying 20~
24h, is placed under tablet machine with 10MPa compactings, and is cut into the electrode slice of 0.6cm × 0.6cm~0.8cm × 0.8cm, with lithium piece
For negative electrode, ethylene carbonate：Dimethyl carbonate：Ethyl methyl carbonate=1:1:8 is electrolyte, in the glove box full of argon
Can be made into lithium half-cell.After testing, the present invention obtained by high conjugation lithium battery carbon silicium cathode material specific capacity be 500~
600mAh/g, obtained lithium ion battery voltage is 4~5V, and energy is 160~180Wh/kg, and with excellent cyclicity
Can, recycling 60~70 times, capability retention is 98~99%.
Compared with additive method, Advantageous Effects are the present invention：
（1）High conjugation lithium battery carbon silicium cathode material obtained by the present invention has higher output voltage, good circulation steady
Qualitative and higher capability retention, and low manufacture cost, storage is abundant, environmental friendliness；
（2）High conjugation lithium battery carbon silicium cathode materials chemistry stability obtained by the present invention is strong, does not react with electrolyte,
Surface energy forms stable thin film, improves the security performance of battery.
Specific embodiment
Discarded rice husk is collected, is cleaned and be dried at being placed in 120~130 DEG C 2~3h, subsequently stood and be cooled to room temperature,
Rice husk will be dried to be placed in ball mill device, 3~5h of ball milling under 250~300r/min, after the completion for the treatment of ball milling, cross 120 mesh sieves, received
Collect to obtain rice husk powder；The rice husk powder of above-mentioned preparation is placed in vacuum pyrolysis device, is led to nitrogen and is excluded air, be subsequently vacuumed out
To 3.5~4.0kPa, 550~600 DEG C, after insulation 10~15min of pyrolysis are warming up to pyrolysis oven by 10 DEG C/min, furnace cooling
To room temperature, pyrolysis rice hull ash is prepared into；In mass ratio 1:5, pyrolysis rice hull ash is mixed with the hydrochloric acid solution of mass fraction 10%,
Under 200~300W after 10~15min of ultrasonic disperse, filter cake, then in mass ratio 1 are filtered and collected:5, by filter cake and mass fraction
20% sodium hydroxide stirring 25~30min of mixing, 10~15min of ultrasonic disperse, is prepared into mixed dispersion liquid under 200~300W；
Count by weight, the mixed dispersion liquid of 45~50 parts of above-mentioned preparations, 10~15 parts of hydrochloric acid of mass fraction 10% and 5 are weighed respectively
~8 parts of dodecylbenzene sodium sulfonate are placed in beaker, 25~30min of stirring mixing at 45~50 DEG C；After the completion of to be mixed, then
The centrifugation under 2500~3000r/min, collects lower sediment and is placed in Muffle furnace, leads to argon and excludes air, 1400
3~5h of calcination processing at~1500 DEG C, cools to room temperature with the furnace, collects calcining mixt and is placed in ball grinder, 250~
3~5h of ball milling under 300r/min, crosses 200 mesh sieves, you can be prepared into a kind of high conjugation lithium battery carbon silicium cathode material.
Example 1
Discarded rice husk is collected, to be cleaned and be dried 2h at being placed in 120 DEG C, subsequently stood and be cooled to room temperature, rice husk will be dried and put
In ball mill device, the ball milling 4h under 250r/min after the completion for the treatment of ball milling, crosses 120 mesh sieves, collects to obtain rice husk powder；Will be above-mentioned
The rice husk powder of preparation is placed in vacuum pyrolysis device, is led to nitrogen and is excluded air, is subsequently vacuumed out to 3.5kPa, by 10 DEG C/min
550 DEG C are warming up to pyrolysis oven, after insulation pyrolysis 10min, room temperature is cooled to the furnace, pyrolysis rice hull ash is prepared into；In mass ratio
1:5, pyrolysis rice hull ash is mixed with the hydrochloric acid solution of mass fraction 10%, under 200W after ultrasonic disperse 10min, filter and collect
Filter cake, then in mass ratio 1:5, filter cake is mixed into 20min with the stirring of the sodium hydroxide of mass fraction 20%, the ultrasonic disperse under 200W
10min, is prepared into mixed dispersion liquid；Count by weight, the mixed dispersion liquid of 45 parts of above-mentioned preparations, 10 parts of quality are weighed respectively
The hydrochloric acid of fraction 10% and 5 parts of dodecylbenzene sodium sulfonate are placed in beaker, the stirring mixing 25min at 45 DEG C；It is to be mixed to complete
Afterwards, then the centrifugation under 2500r/min, collect lower sediment to be placed in Muffle furnace, lead to argon and exclude air, at 1400 DEG C
Lower calcination processing 3h, cools to room temperature with the furnace, collects calcining mixt and is placed in ball grinder, the ball milling 3h under 250r/min,
Cross 200 mesh sieves, you can be prepared into a kind of high conjugation lithium battery carbon silicium cathode material.
By the high conjugation lithium battery carbon silicium cathode material obtained by the present invention and conductive agent acetylene black, binding agent PVDF with 6:
1:1 uniform quality mixing, in the environment of ambient humidity is for 10%, is applied on Copper Foil simultaneously by solvent of N-Methyl pyrrolidone
Dry under heat lamp, be subsequently transferred to dry 20h in 120 DEG C of baking oven, be placed under tablet machine with 10MPa compactings, and be cut into
The electrode slice of 0.6cm × 0.6cm, with lithium piece as negative electrode,：Ethylene carbonate：Dimethyl carbonate：Ethyl methyl carbonate=1:1:8 are
Electrolyte, in the glove box full of argon lithium half-cell is can be made into.After testing, the high conjugation lithium battery obtained by the present invention
The specific capacity of carbon silicium cathode material is 500mAh/g, and obtained lithium ion battery voltage is 4V, and energy is 160Wh/kg, and is had
There is excellent cycle performance, recycle 60 times, capability retention is 98%.
Example 2
Discarded rice husk is collected, to be cleaned and be dried 3h at being placed in 130 DEG C, subsequently stood and be cooled to room temperature, rice husk will be dried and put
In ball mill device, the ball milling 5h under 300r/min after the completion for the treatment of ball milling, crosses 120 mesh sieves, collects to obtain rice husk powder；Will be above-mentioned
The rice husk powder of preparation is placed in vacuum pyrolysis device, is led to nitrogen and is excluded air, is subsequently vacuumed out to 4.0kPa, by 10 DEG C/min
600 DEG C are warming up to pyrolysis oven, after insulation pyrolysis 15min, room temperature is cooled to the furnace, pyrolysis rice hull ash is prepared into；In mass ratio
1:5, pyrolysis rice hull ash is mixed with the hydrochloric acid solution of mass fraction 10%, under 300W after ultrasonic disperse 15min, filter and collect
Filter cake, then in mass ratio 1:5, filter cake is mixed into 30min with the stirring of the sodium hydroxide of mass fraction 20%, the ultrasonic disperse under 300W
15min, is prepared into mixed dispersion liquid；Count by weight, the mixed dispersion liquid of 50 parts of above-mentioned preparations, 15 parts of quality are weighed respectively
The hydrochloric acid of fraction 10% and 8 parts of dodecylbenzene sodium sulfonate are placed in beaker, the stirring mixing 30min at 50 DEG C；It is to be mixed to complete
Afterwards, then the centrifugation under 3000r/min, collect lower sediment to be placed in Muffle furnace, lead to argon and exclude air, at 1500 DEG C
Lower calcination processing 5h, cools to room temperature with the furnace, collects calcining mixt and is placed in ball grinder, the ball milling 5h under 300r/min,
Cross 200 mesh sieves, you can be prepared into a kind of high conjugation lithium battery carbon silicium cathode material.
By the high conjugation lithium battery carbon silicium cathode material obtained by the present invention and conductive agent acetylene black, binding agent PVDF with 8:
1:1 uniform quality mixing, in the environment of ambient humidity is for 15%, is applied on Copper Foil simultaneously by solvent of N-Methyl pyrrolidone
Dry under heat lamp, be subsequently transferred to dry 24h in 120 DEG C of baking oven, be placed under tablet machine with 10MPa compactings, and be cut into
The electrode slice of 0.8cm × 0.8cm, with lithium piece as negative electrode, ethylene carbonate：Dimethyl carbonate：Ethyl methyl carbonate=1:1:8 are
Electrolyte, in the glove box full of argon lithium half-cell is can be made into.After testing, the high conjugation lithium battery obtained by the present invention
The specific capacity of carbon silicium cathode material is 600mAh/g, and obtained lithium ion battery voltage is 5V, and energy is 180Wh/kg, and is had
There is excellent cycle performance, recycle 70 times, capability retention is 99%.
Example 3
Discarded rice husk is collected, to be cleaned and be dried 3h at being placed in 125 DEG C, subsequently stood and be cooled to room temperature, rice husk will be dried and put
In ball mill device, the ball milling 4h under 275r/min after the completion for the treatment of ball milling, crosses 120 mesh sieves, collects to obtain rice husk powder；Will be above-mentioned
The rice husk powder of preparation is placed in vacuum pyrolysis device, is led to nitrogen and is excluded air, is subsequently vacuumed out to 3.7kPa, by 10 DEG C/min
575 DEG C are warming up to pyrolysis oven, after insulation pyrolysis 13min, room temperature is cooled to the furnace, pyrolysis rice hull ash is prepared into；In mass ratio
1:5, pyrolysis rice hull ash is mixed with the hydrochloric acid solution of mass fraction 10%, under 250W after ultrasonic disperse 12min, filter and collect
Filter cake, then in mass ratio 1:5, filter cake is mixed into 27min with the stirring of the sodium hydroxide of mass fraction 20%, the ultrasonic disperse under 250W
13min, is prepared into mixed dispersion liquid；Count by weight, the mixed dispersion liquid of 47 parts of above-mentioned preparations, 13 parts of quality are weighed respectively
The hydrochloric acid of fraction 10% and 7 parts of dodecylbenzene sodium sulfonate are placed in beaker, the stirring mixing 28min at 43 DEG C；It is to be mixed to complete
Afterwards, then the centrifugation under 2750r/min, collect lower sediment to be placed in Muffle furnace, lead to argon and exclude air, at 1450 DEG C
Lower calcination processing 4h, cools to room temperature with the furnace, collects calcining mixt and is placed in ball grinder, the ball milling 4h under 275r/min,
Cross 200 mesh sieves, you can be prepared into a kind of high conjugation lithium battery carbon silicium cathode material.
By the high conjugation lithium battery carbon silicium cathode material obtained by the present invention and conductive agent acetylene black, binding agent PVDF with 7:
1:1 uniform quality mixing, in the environment of ambient humidity is for 13%, is applied on Copper Foil simultaneously by solvent of N-Methyl pyrrolidone
Dry under heat lamp, be subsequently transferred to dry 22h in 120 DEG C of baking oven, be placed under tablet machine with 10MPa compactings, and be cut into
The electrode slice of 0.7cm × 0.7cm, with lithium piece as negative electrode, ethylene carbonate：Dimethyl carbonate：Ethyl methyl carbonate=1:1:8 are
Electrolyte, in the glove box full of argon lithium half-cell is can be made into.After testing, the high conjugation lithium battery obtained by the present invention
The specific capacity of carbon silicium cathode material is 550mAh/g, and obtained lithium ion battery voltage is 4.5V, and energy is 170Wh/kg, and
With excellent cycle performance, recycle 65 times, capability retention is 98.5%.
Claims (1)
1. a kind of preparation method of high conjugation lithium battery carbon silicium cathode material, it is characterised in that concrete preparation process is：
（1）Discarded rice husk is collected, is cleaned and be dried at being placed in 120~130 DEG C 2~3h, subsequently stood and be cooled to room temperature, will
It is dried rice husk to be placed in ball mill device, 3~5h of ball milling under 250~300r/min, after the completion for the treatment of ball milling, crosses 120 mesh sieves, collects
Obtain rice husk powder；
（2）The rice husk powder of above-mentioned preparation is placed in vacuum pyrolysis device, is led to nitrogen and is excluded air, be subsequently vacuumed out to 3.5
~4.0kPa, by 10 DEG C/min 550~600 DEG C are warming up to pyrolysis oven, after insulation 10~15min of pyrolysis, cool to room with the furnace
Temperature, is prepared into pyrolysis rice hull ash；
（3）In mass ratio 1:5, pyrolysis rice hull ash is mixed with the hydrochloric acid solution of mass fraction 10%, the ultrasound point under 200~300W
After dissipating 10~15min, filter cake, then in mass ratio 1 are filtered and collected:5, filter cake and the stirring of the sodium hydroxide of mass fraction 20% is mixed
25~30min is closed, 10~15min of ultrasonic disperse, is prepared into mixed dispersion liquid under 200~300W；
（4）Count by weight, the mixed dispersion liquid of 45~50 parts of above-mentioned preparations, 10~15 parts of mass fractions 10% are weighed respectively
Hydrochloric acid and 5~8 parts of dodecylbenzene sodium sulfonate are placed in beaker, 25~30min of stirring mixing at 45~50 DEG C；
（5）After the completion of to be mixed, then the centrifugation under 2500~3000r/min, collect lower sediment and be placed in Muffle furnace,
Logical argon excludes air, and 3~5h of calcination processing at 1400~1500 DEG C cools to room temperature with the furnace, collects calcining mixt simultaneously
In being placed in ball grinder, 3~5h of ball milling under 250~300r/min crosses 200 mesh sieves, you can be prepared into a kind of high conjugation lithium electricity
Pond carbon silicium cathode material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109768249A (en) * | 2019-01-04 | 2019-05-17 | 蜂巢能源科技有限公司 | Negative electrode material of lithium ion battery and preparation method thereof and lithium ion battery |
| CN110713188A (en) * | 2019-10-18 | 2020-01-21 | 中国石油大学(华东) | Method for preparing silicon-carbon negative electrode material for lithium ion battery from rice hulls |
| CN112635742A (en) * | 2020-12-29 | 2021-04-09 | 惠州锂威新能源科技有限公司 | Preparation method of carbon-silicon negative electrode material of lithium ion battery, negative electrode material and lithium ion battery |
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| CN105098183A (en) * | 2014-05-21 | 2015-11-25 | 长春市朗欢科技有限公司 | Preparation for carbon anode material of lithium ion battery by using rice hull as raw material |
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| CN109768249B (en) * | 2019-01-04 | 2021-05-25 | 蜂巢能源科技有限公司 | Negative electrode material of lithium ion battery, preparation method of negative electrode material and lithium ion battery |
| CN110713188A (en) * | 2019-10-18 | 2020-01-21 | 中国石油大学(华东) | Method for preparing silicon-carbon negative electrode material for lithium ion battery from rice hulls |
| CN112635742A (en) * | 2020-12-29 | 2021-04-09 | 惠州锂威新能源科技有限公司 | Preparation method of carbon-silicon negative electrode material of lithium ion battery, negative electrode material and lithium ion battery |
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| CN106684336B (en) | 2019-08-23 |
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