CN109638269A - A kind of silicon/expanded graphite/agraphitic carbon composite material and preparation method - Google Patents
A kind of silicon/expanded graphite/agraphitic carbon composite material and preparation method Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of silicon/expanded graphite/agraphitic carbon composite material, and ethyl orthosilicate, dehydrated alcohol and deionized water are mixed, and oxalic acid solution and ammonium hydroxide is added dropwise, and form alcogel, aging, supercritical drying obtain SiO2Aeroge blocks of solid, mixes with magnesium powder, heats under an argon atmosphere, places into HCl solution and HF solution after cooling, impregnates, cleaning, drying, obtains nano-structure porous silicon；Then nano-structure porous silicon mixed in ethanol with expanded graphite, stirred, impregnated, filtered, finally coated under protective atmosphere, obtain silicon/expanded graphite/agraphitic carbon composite material.The present invention solves the problems, such as poor circulation caused by the huge bulk effect of silicium cathode in the prior art.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of lithium ion battery negative material and its preparation side
Method.
Background technique
Silicon based anode material has highest lithium storage content and lower voltage platform, be most potential next-generation lithium from
One of sub- cell negative electrode material.However, silicium cathode has huge bulk effect, the mechanism that huge bulk effect generates
Power can make between electrode active material and collector gradually to disengage and silicon activity mutually itself also can dusting, to lose and afflux
The electrical contact of body causes electrode cycle performance to decline rapidly；And silicon itself is semiconductor material, and intrinsic conductivity is low.
Summary of the invention
The purpose of the invention is to overcome the deficiencies of the prior art and provide a kind of new porous Si-C composite material and its
Preparation method.
The present invention is achieved by the following technical programs:
A kind of preparation method of silicon/expanded graphite/agraphitic carbon composite material, comprising the following steps:
A1、SiO2The preparation of aeroge: ethyl orthosilicate, dehydrated alcohol and deionized water are mixed, stirred evenly, slowly
Oxalic acid solution, which is added dropwise, makes its hydrolysis, then ammonium hydroxide is added dropwise and stirs evenly, and standing forms alcogel, and alcogel sealing is then placed on perseverance
Aging in tepidarium finally carries out supercritical drying to alcogel, obtains SiO2 gas to obtain high-intensitive dimensional network structure
Gel blocks of solid；
The preparation of A2, nano-structure porous silicon: SiO2 aeroge blocks of solid and magnesium powder are mixed, are heated to 600- under an argon atmosphere
900 DEG C, 1-5h is kept the temperature, is placed into HCl solution after cooling, the MgO being attached on solid particle is removed, is then immersed in HF solution
In, 10min is impregnated, cleaning is taken out, dries to get nano-structure porous silicon is arrived；
A3, porous silicon/expanded graphite composite precursor: the nano-structure porous silicon of preparation and expanded graphite are mixed in ethanol
It closes, stirring, then takes out slurry and impregnated, be embedded into nano-structure porous silicon in expanded graphite, porous silicon/swollen is obtained after filtering
Swollen graphite composite precursor；
A4, cladding: porous silicon/expanded graphite composite precursor is coated under protective atmosphere, and cladding mode is solid phase packet
It covers, liquid phase coating or gas phase cladding, cladding carbon source is one of pitch, glucose, methane, acetylene or a variety of, cladding carbonization
Afterwards, silicon/expanded graphite/agraphitic carbon composite material is obtained.
Preferably, in step A1, the ethyl orthosilicate, dehydrated alcohol and deionized water in mass ratio 1: 6: 4 is mixed
It closes；
Preferably, in step A1, the concentration of the oxalic acid solution is 0.01mol/L, and the concentration of the ammonium hydroxide is 0.1mol/L；
Preferably, in step A2, by the SiO of preparation2Aeroge blocks of solid and magnesium powder 2.5-5: 1 are respectively put into two in molar ratio
In a special steel boat, then steel boat is put into the container of argon gas protection and is sealed, the container of sealing is then put into tube furnace
In, it is warming up to 600-900 DEG C under an argon atmosphere, keeps the temperature 1-5h, then cools to room temperature, it is molten that taking-up blocks of solid is put into HCl
In liquid, 4-8h is stood under room temperature, is removed the MgO being attached on solid particle, is then immersed in HF solution, takes out after soaking and washing
It dries to get nano-structure porous silicon is arrived.
Preferably, in step A2, the concentration of the HCl solution is 6mol/L, and the concentration of the HF solution is 15mol/L.
Preferably, in step A3, the nano-structure porous silicon of preparation and expanded graphite are carried out in ethanol by 1-5:1 mass ratio
Mixing stirs 4h by circular pan mixer, takes out slurry by impregnating equipment and impregnates 1-5h, is embedded into nano-structure porous silicon swollen
In swollen graphite, filtering obtains porous silicon/expanded graphite composite precursor.
Preferably, in step A3, the expansion multiple of the expanded graphite is 200-300 times.
Preferably, in step A4, by porous silicon/expanded graphite composite precursor in rotary furnace, pushed bat kiln, roller kilns into
Row cladding, cladding mode are solid phase cladding, liquid phase coating or gas phase cladding, and cladding carbon source is pitch, glucose, methane, acetylene
One of or it is a variety of, cladding ratio be 2%-10%, be coated under protective atmosphere and carry out, the protective atmosphere be nitrogen or argon
The mixed atmosphere of gas or nitrogen and argon gas, cladding carburizing temperature are 700-1200 DEG C, carry out carbonization 2h, obtain silicon/expansion stone
Ink/agraphitic carbon composite material.
Of the invention has following technical effect that
The present invention uses silicon-porous silicon-insertion expanded graphite-cladding agraphitic carbon manufacture craft route, prepares silicon/expansion
Graphite/agraphitic carbon composite material, structure are as shown in Figure 1 and Figure 2.It is huge that the present invention solves silicium cathode in the prior art
The problem of poor circulation caused by bulk effect and silicon intrinsic conductivity, are low, are directly used as poorly conductive when cathode
Problem.
The present invention uses expanded graphite, and conductivity is high, and carbon-to-carbon interlamellar spacing is big, biggish after Si is embedded in expanded graphite inside
Interlamellar spacing provides enough spaces for the storage and volume expansion of Si, or remote lithium ion transport provides conductive mesh
Network.
Porous silicon in the present invention has bigger specific surface area and cellular structure abundant, and silicon has been effectively relieved in charge and discharge
Volume expansion blockage effect in electric process, improves the comprehensive performance of material.
Silicon/expanded graphite/agraphitic carbon composite material excellent electrochemical performance is mainly abundant inside second particle
The stress of silicon volume change generation, also, expanded graphite and unformed can be absorbed in cellular structure and the flexibility of expanded graphite
Carbon can provide channel for the quick transmission of lithium ion and electronics.
Detailed description of the invention
Fig. 1 is silicon/expanded graphite/agraphitic carbon composite material structural schematic diagram.
Fig. 2 is porous silicon/expanded graphite composite precursor scanning electron microscope (SEM) photograph.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1
Step 1, at room temperature, ethyl orthosilicate, dehydrated alcohol and deionized water in mass ratio 1: 6: 4 is mixed evenly, and is delayed
The slow 0.01mol/L oxalic acid solution that is added dropwise makes its hydrolysis, then the ammonium hydroxide of 0.1mol/L is added dropwise and stirs evenly, and standing forms alcogel.
Alcogel sealing is placed on aging in 50 DEG C of water bath with thermostatic control, to obtain high-intensitive dimensional network structure.Finally to gel into
Row supercritical drying obtains SiO2 aeroge blocks of solid.
SiO2 aeroge blocks of solid and magnesium powder are put into two special steel boats with molar ratio 2.5:1 mixing by step 2
In, then steel boat is put into the container of argon gas protection and is sealed, then the container of sealing is put into tube furnace, in argon atmosphere
Under be warming up to 600 DEG C, be cooled to room temperature after keeping the temperature 1 h, then in HCl solution, 4 h stood under room temperature, removal is attached to solid
MgO on particle is finally immersed in HF solution, impregnates 10min, is taken out after cleaning and is dried obtained nano-structure porous silicon (partial size
100nm)。
Step 3 is mixed the porous silicon of preparation and expanded graphite (200 times of expansion multiple) in 1:1 ratio in filtering ethyl alcohol
It closes and 4h is stirred by circular pan mixer, take out slurry by impregnating equipment, impregnate 1h, nano-structure porous silicon is impregnated into expansion stone
Porous silicon/expanded graphite composite precursor is obtained by filtration in Mo Zhong.
Step 4 will prepare gained porous silicon/expanded graphite composite precursor in rotary furnace using nitrogen as protective atmosphere, drip
Blueness is that carbon source is coated, and cladding ratio is 2%, and cladding carburizing temperature is 700 DEG C, and heating rate is 2 DEG C/min, and be carbonized 2h, is obtained
To silicon/expanded graphite/agraphitic carbon composite material.
Embodiment 2
Step 1, at room temperature, ethyl orthosilicate, dehydrated alcohol and deionized water in mass ratio 1: 6: 4 is mixed evenly, and is delayed
Slowly a certain amount of 0.01mol/L oxalic acid solution, which is added dropwise, makes its hydrolysis, then the ammonium hydroxide of 0.1mol/L is added dropwise and stirs evenly, and standing forms alcohol
Gel.It is sealed against being placed on aging in 50 DEG C of water bath with thermostatic control, to obtain high-intensitive dimensional network structure.Finally to gel into
Row supercritical drying, obtains SiO2Aeroge blocks of solid.
Step 2, by SiO2Aeroge blocks of solid and magnesium powder 5:1 mixing in molar ratio are put into two special steel boats,
Steel boat is put into again in the container of argon gas protection and is sealed, then the container of sealing is put into tube furnace, under an argon atmosphere
900 DEG C are warming up to, is cooled to room temperature after keeping the temperature 5h, then in HCl solution, 8h is stood under room temperature, removal is attached to solid particle
On MgO, be finally immersed in HF solution, impregnate 10min, after cleaning take out drying, be made nano-structure porous silicon (partial size
200nm)。
Step 3, by the porous silicon of preparation and expanded graphite (250 times of expansion multiple) 2:1 in mass ratio in filtering ethyl alcohol
Mixing stirs 4h by circular pan mixer, takes out slurry by impregnating equipment, impregnates 2h, nano-structure porous silicon is impregnated into swollen
In swollen graphite, porous silicon/expanded graphite composite precursor is obtained by filtration.
Step 4, will preparation gained porous silicon/expanded graphite composite precursor in rotary furnace using nitrogen as protective atmosphere, Portugal
Grape sugar is that carbon source is coated, and cladding ratio is 10%, and cladding carburizing temperature is 1200 DEG C, and heating rate is 10 DEG C/min, carbonization
2h obtains silicon/expanded graphite/agraphitic carbon composite material.
Embodiment 3
Step 1, at room temperature, ethyl orthosilicate, dehydrated alcohol and deionized water in mass ratio 1: 6: 4 is mixed evenly, and is delayed
Slowly a certain amount of 0.01mol/L oxalic acid solution, which is added dropwise, makes its hydrolysis, then the ammonium hydroxide of 0.1mol/L is added dropwise and stirs evenly, and standing forms alcohol
Gel.It is sealed against being placed on aging in 50 DEG C of water bath with thermostatic control, to obtain high-intensitive dimensional network structure.Finally to gel into
Row supercritical drying, obtains SiO2Aeroge blocks of solid.
Step 2, by SiO2Aeroge blocks of solid and magnesium powder are put into two special steel boats with molar ratio 3:1 mixing,
Steel boat is put into again in the container of argon gas protection and is sealed, then the container of sealing is put into tube furnace, under an argon atmosphere
700 DEG C are warming up to, is cooled to room temperature after keeping the temperature 2h, then in HCl solution, 5h is stood under room temperature, removal is attached to solid particle
On MgO, be finally immersed in HF solution, impregnate 10min, after cleaning take out dry be made nano-structure porous silicon (partial size 170nm).
Step 3 is mixed the porous silicon of preparation and expanded graphite (300 times of expansion multiple) in 5:1 ratio in filtering ethyl alcohol
It closes and 4h is stirred by circular pan mixer, take out slurry by impregnating equipment, impregnate 3h, nano-structure porous silicon is impregnated into expansion stone
Porous silicon/expanded graphite composite precursor is obtained by filtration in Mo Zhong.
Step 4 will prepare gained porous silicon/expanded graphite composite precursor in rotary furnace using nitrogen as protective atmosphere, drip
Blueness is that carbon source is coated, and cladding ratio is 4%, and cladding carburizing temperature is 900 DEG C, and heating rate is 4 DEG C/min, and be carbonized 2h, is obtained
To silicon/expanded graphite/agraphitic carbon composite material.
Embodiment 4
Step 1, at room temperature, ethyl orthosilicate, dehydrated alcohol and deionized water in mass ratio 1: 6: 4 is mixed evenly, and is delayed
Slowly a certain amount of 0.01mol/L oxalic acid solution, which is added dropwise, makes its hydrolysis, then the ammonium hydroxide of 0.1mol/L is added dropwise and stirs evenly, and standing forms alcohol
Gel.It is sealed against being placed on aging in 50 DEG C of water bath with thermostatic control, to obtain high-intensitive dimensional network structure.Finally to gel into
Row supercritical drying, obtains SiO2Aeroge blocks of solid.
Step 2, by SiO2Aeroge blocks of solid and magnesium powder are mixed with molar ratio 3.5:1 is put into two special steel boats
In, then steel boat is put into the container of argon gas protection and is sealed, then the container of sealing is put into tube furnace, in argon atmosphere
Under be warming up to 650 DEG C, be cooled to room temperature after keeping the temperature 3h, then in HCl solution, 6h stood under room temperature, removal is attached to solid
MgO on grain is finally immersed in HF solution, impregnates 10min, is taken out after cleaning and is dried obtained nano-structure porous silicon (partial size
350nm)。
Step 3 is mixed the porous silicon of preparation and expanded graphite (220 times of expansion multiple) in 3:1 ratio in filtering ethyl alcohol
It closes and 4h is stirred by circular pan mixer, take out slurry by impregnating equipment, impregnate 4h, nano-structure porous silicon is impregnated into expansion stone
Porous silicon/expanded graphite composite precursor is obtained by filtration in Mo Zhong.
Step 4 will prepare gained porous silicon/expanded graphite composite precursor in rotary furnace using nitrogen as protective atmosphere, drip
Blueness is that carbon source is coated, and cladding ratio is 6%, and cladding carburizing temperature is 800 DEG C, and heating rate is 6 DEG C/min, and be carbonized 2h, is obtained
To silicon/expanded graphite/agraphitic carbon composite material.
Embodiment 5
Step 1, at room temperature, ethyl orthosilicate, dehydrated alcohol and deionized water in mass ratio 1: 6: 4 is mixed evenly, and is delayed
Slowly a certain amount of 0.01mol/L oxalic acid solution, which is added dropwise, makes its hydrolysis, then the ammonium hydroxide of 0.1mol/L is added dropwise and stirs evenly, and standing forms alcohol
Gel.It is sealed against being placed on aging in 50 DEG C of water bath with thermostatic control, to obtain high-intensitive dimensional network structure.Finally to gel into
Row supercritical drying, obtains SiO2Aeroge blocks of solid.
Step 2, by SiO2Aeroge blocks of solid and magnesium powder are put into two special steel boats with molar ratio 4:1 mixing,
Steel boat is put into again in the container of argon gas protection and is sealed, then the container of sealing is put into tube furnace and is risen under an argon atmosphere
Temperature is cooled to room temperature after keeping the temperature 4h to 800 DEG C, then in HCl solution, 7h is stood under room temperature, removal is attached on solid particle
MgO, be finally immersed in HF solution, impregnate 10min, after cleaning take out dry be made nano-structure porous silicon (partial size 300nm).
Step 3 is mixed the porous silicon of preparation and expanded graphite (270 times of expansion multiple) in 4:1 ratio in filtering ethyl alcohol
It closes and 4h is stirred by circular pan mixer, take out slurry by impregnating equipment, impregnate 5h, nano-structure porous silicon is impregnated into expansion stone
Porous silicon/expanded graphite composite precursor is obtained by filtration in Mo Zhong.
Step 4 will prepare gained porous silicon/expanded graphite composite precursor in rotary furnace using nitrogen as protective atmosphere, drip
Blueness is that carbon source is coated, and cladding ratio is 8%, and cladding carburizing temperature is 1000 DEG C, and heating rate is 8 DEG C/min, and be carbonized 2h,
Obtain silicon/expanded graphite/agraphitic carbon composite material.
Embodiment 6
Step 1, at room temperature, ethyl orthosilicate, dehydrated alcohol and deionized water in mass ratio 1: 6: 4 is mixed evenly, and is delayed
Slowly a certain amount of 0.01mol/L oxalic acid solution, which is added dropwise, makes its hydrolysis, then the ammonium hydroxide of 0.1mol/L is added dropwise and stirs evenly, and standing forms alcohol
Gel.It is sealed against being placed on aging in 50 DEG C of water bath with thermostatic control, to obtain high-intensitive dimensional network structure.Finally to gel into
Row supercritical drying, obtains SiO2Aeroge blocks of solid.
Step 2, by SiO2Aeroge blocks of solid and magnesium powder are mixed with molar ratio 4.5:1 is put into two special steel boats
In, then steel boat is put into the container of argon gas protection and is sealed, then the container of sealing is put into tube furnace, in argon atmosphere
Under be warming up to 750 DEG C, be cooled to room temperature after keeping the temperature 2.5h, then in HCl solution, 4h stood under room temperature, removal is attached to solid
MgO on particle is finally immersed in HF solution, impregnates 10min, is taken out after cleaning and is dried obtained nano-structure porous silicon (partial size
240nm)。
Step 3 is mixed the porous silicon of preparation and expanded graphite (200 times of expansion multiple) in 5:1 ratio in filtering ethyl alcohol
It closes and 4h is stirred by circular pan mixer, take out slurry by impregnating equipment, impregnate 3h, nano-structure porous silicon is impregnated into expansion stone
Porous silicon/expanded graphite composite precursor is obtained by filtration in Mo Zhong.
Step 4 will prepare gained porous silicon/expanded graphite composite precursor in rotary furnace using nitrogen as protective atmosphere, drip
Blueness is that carbon source is coated, and cladding ratio is 5%, and cladding carburizing temperature is 1100 DEG C, and heating rate is 9 DEG C/min, and be carbonized 2h,
Obtain silicon/expanded graphite/agraphitic carbon composite material.
Silicon/expanded graphite/agraphitic carbon composite material of above-described embodiment 1-6 preparation is tested for the property, result
It is as shown in the table:
| Powder body compacted density (g/cm3) | Reversible capacity (mAh/g) for the first time | Coulombic efficiency (%) for the first time | 50 capacity retention ratios (%) of 10C charge and discharge cycles | |
| Embodiment 1 | 1.403 | 926 | 82.40% | 76.32% |
| Embodiment 2 | 1.236 | 1086 | 80.6% | 77.4% |
| Embodiment 3 | 1.421 | 1287 | 81.23% | 75.26% |
| Embodiment 4 | 1.460 | 1145 | 82.32% | 74.33% |
| Embodiment 5 | 1.432 | 1197 | 80.56% | 76.85% |
| Embodiment 6 | 1.475 | 1259 | 81.65% | 74.56% |
As can be seen from the above table, silicon/expanded graphite/agraphitic carbon composite material prepared by the present invention has good cyclicity
Energy.
Claims (8)
1. a kind of preparation method of silicon/expanded graphite/agraphitic carbon composite material, which comprises the following steps:
A1、SiO2The preparation of aeroge: ethyl orthosilicate, dehydrated alcohol and deionized water are mixed, stirred evenly, slowly
Oxalic acid solution is added dropwise, adjusting pH is that 2-5 accelerates hydrolysis rate, then ammonium hydroxide is added dropwise and is greater than 7 to pH, accelerates polycondensation reaction, stirring is equal
Even, standing forms alcogel, and alcogel sealing is then placed on aging in water bath with thermostatic control, to obtain high-intensitive cubic network knot
Structure finally carries out supercritical drying to alcogel, obtains SiO2 aeroge blocks of solid；
The preparation of A2, nano-structure porous silicon: SiO2 aeroge blocks of solid and magnesium powder are mixed, are heated to 600- under an argon atmosphere
900 DEG C, 1-5h is kept the temperature, is placed into HCl solution after being cooled to room temperature, removed the MgO being attached on solid particle, be then immersed in
It is impregnated in HF solution, takes out cleaning, dries to get nano-structure porous silicon is arrived；
A3, porous silicon/expanded graphite composite precursor: the nano-structure porous silicon of preparation and expanded graphite are mixed in ethanol
Conjunction, stirring form slurry, then take out slurry and are impregnated, be embedded into nano-structure porous silicon in expanded graphite, obtain after filtering
Porous silicon/expanded graphite composite precursor；
A4, cladding: porous silicon/expanded graphite composite precursor is coated under protective atmosphere, and cladding mode is solid phase packet
It covers, liquid phase coating or gas phase cladding, cladding carbon source is one of pitch, glucose, methane, acetylene or a variety of, cladding carbonization
Afterwards, silicon/expanded graphite/agraphitic carbon composite material is obtained.
2. a kind of preparation method of silicon/expanded graphite/agraphitic carbon composite material according to claim 1, feature exist
In: in step A1, the ethyl orthosilicate, dehydrated alcohol and deionized water in mass ratio 1: 6: 4 is mixed.
3. a kind of preparation method of silicon/expanded graphite/agraphitic carbon composite material according to claim 1, feature exist
In: in step A1, the concentration of the oxalic acid solution is 0.01mol/L, and the concentration of the ammonium hydroxide is 0.1mol/L.
4. a kind of preparation method of silicon/expanded graphite/agraphitic carbon composite material according to claim 1, feature exist
In: in step A2, by the SiO2 aeroge blocks of solid and magnesium powder of preparation in molar ratio 2.5-5: 1 be respectively put into two it is special
In steel boat, then steel boat is put into the container of argon gas protection and is sealed, then the container of sealing is put into tube furnace, in argon gas
It is warming up to 600-900 DEG C under atmosphere, keeps the temperature 1-5h, then cools to room temperature, takes out blocks of solid and is put into HCl solution, room temperature
Lower standing 4-8h removes the MgO that is attached on solid particle, is then immersed in HF solution, taken out after soaking and washing drying to get
To nano-structure porous silicon.
5. a kind of preparation method of silicon/expanded graphite/agraphitic carbon composite material according to claim 1, feature exist
In: in step A2, the concentration of the HCl solution is 6mol/L, and the concentration of the HF solution is 15mol/L.
6. a kind of preparation method of silicon/expanded graphite/agraphitic carbon composite material according to claim 1, feature exist
In: in step A3, the nano-structure porous silicon of preparation is mixed with expanded graphite by 1-5:1 mass ratio in ethanol, passes through circle
Pan mixer stirs 4h, takes out slurry by impregnating equipment and impregnates 1-5h, is embedded into nano-structure porous silicon in expanded graphite, mistake
Filter, obtains porous silicon/expanded graphite composite precursor.
7. a kind of preparation method of silicon/expanded graphite/agraphitic carbon composite material according to claim 1, feature exist
In: in step A3, the expansion multiple of the expanded graphite is 200-300 times.
8. a kind of preparation method of silicon/expanded graphite/agraphitic carbon composite material according to claim 1, feature exist
In: in step A4, porous silicon/expanded graphite composite precursor is coated in rotary furnace, pushed bat kiln, roller kilns, is coated
Mode is solid phase cladding, liquid phase coating or gas phase cladding, and cladding carbon source is one of pitch, glucose, methane, acetylene or more
Kind, cladding ratio is 2%-10%, is coated under protective atmosphere and carries out, and the protective atmosphere is nitrogen or argon gas or nitrogen and argon
The mixed atmosphere of gas, cladding carburizing temperature are 700-1200 DEG C, carry out carbonization 2h, it is compound to obtain silicon/expanded graphite/agraphitic carbon
Material.
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| CN110606757A (en) * | 2019-09-23 | 2019-12-24 | 长兴兴鹰新型耐火建材有限公司 | Sulfur-alkali corrosion resistant wear-resistant castable for sludge incineration kiln and preparation process thereof |
| CN114122341A (en) * | 2020-08-31 | 2022-03-01 | 贝特瑞新材料集团股份有限公司 | Silicon-based composite material, preparation method thereof and lithium ion battery |
| CN114188512A (en) * | 2020-09-14 | 2022-03-15 | 湖南中科星城石墨有限公司 | Silicon-carbon composite material and preparation method and application thereof |
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| CN110571415A (en) * | 2019-08-15 | 2019-12-13 | 中南大学 | silicon-carbon negative electrode material and preparation method thereof |
| CN110606757A (en) * | 2019-09-23 | 2019-12-24 | 长兴兴鹰新型耐火建材有限公司 | Sulfur-alkali corrosion resistant wear-resistant castable for sludge incineration kiln and preparation process thereof |
| CN110606757B (en) * | 2019-09-23 | 2022-02-25 | 长兴兴鹰新型耐火建材有限公司 | Sulfur-alkali corrosion resistant wear-resistant castable for sludge incineration kiln and preparation process thereof |
| CN114122341A (en) * | 2020-08-31 | 2022-03-01 | 贝特瑞新材料集团股份有限公司 | Silicon-based composite material, preparation method thereof and lithium ion battery |
| EP3985759A4 (en) * | 2020-08-31 | 2022-09-21 | Btr New Material Group Co., Ltd. | Silicon-based composite material, negative electrode, lithium ion battery and preparation method |
| JP2022549748A (en) * | 2020-08-31 | 2022-11-29 | 貝特瑞新材料集団股▲ふん▼有限公司 | Silicon-based composite material, negative electrode, lithium-ion battery, and manufacturing method |
| JP7455870B2 (en) | 2020-08-31 | 2024-03-26 | 貝特瑞新材料集団股▲ふん▼有限公司 | Silicon-based composite material, negative electrode, lithium ion battery, and manufacturing method |
| CN114188512A (en) * | 2020-09-14 | 2022-03-15 | 湖南中科星城石墨有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN114188512B (en) * | 2020-09-14 | 2024-02-27 | 湖南中科星城石墨有限公司 | Silicon-carbon composite material and preparation method and application thereof |
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Address after: Jinzhou 410600 Hunan province Ningxiang County District Changsha Quan Zhou Bei Lu (Jin Zhou Zhen Long Qiao Cun) Applicant after: Hunan Branch Star graphite Co. Address before: 410600 Quanzhou North Road, Jinzhou New District, Ningxiang County, Zhuzhou City, Hunan Province Applicant before: Hunan Branch Star graphite Co. |
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Application publication date: 20190416 |