CN108923037A - A kind of Silicon-rich SiOx-C material and its preparation method and application - Google Patents
A kind of Silicon-rich SiOx-C material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of Silicon-rich SiOxThe preparation method of C-material becomes SiO by the group that etching SiO disproportionated reaction generates using SiO as raw material2The SiO of@SiO@SixPorous silicon-base material is obtained, CVD is then passed through（Chemical vapor deposition）Method deposits Si in the pore structure of porous silicon-base material, to obtain the SiO of Silicon-richxMaterial, and the carbon coating layer further formed by CVD deposition.The Silicon-rich SiO of preparation method preparation through the inventionxThe gram volume of C-material and for the first time coulombic efficiency are above commercialized SiO, and cyclical stability is relatively preferable, overcome SiO material head and imitate lower defect.
Description
Technical field
The invention belongs to field of lithium ion battery, and in particular to a kind of Silicon-rich SiOxIt C-material and preparation method thereof and answers
With.
Background technique
In recent years, it is answered with lithium ion battery in the powerful devices such as electric tool, electronic/mixed electrical automobile, energy-accumulating power station
With continuous expansion, conventional graphite cathode（Specific capacity 372mAh/g）The mankind it have been difficult to meet to high energy density cells
Demand, therefore the next-generation lithium ion battery anode material that can substitute graphite is found as current lithium ion battery correlative study
One of hot spot.The theoretical specific capacity of silicon materials is 4200mAh/g, resourceful, solvent will not occur with electrolyte and be embedded in altogether
Phenomenon, while intercalation potential is higher, it is safer.However silicon anode material can undergo up to 300% body in charge and discharge process
Product variation, so high volume expansion are shunk, and are easily led to electrode material crushing, are disengaged with collector, electrodes conduct network,
Volume change brings the generation on new surface simultaneously, needs to form new solid-electrolyte interface（SEI）So as to cause to electrolyte
A large amount of consumption, and then lead to being greatly lowered for cycle life.On the other hand, the conductivity of silicon, lithium ion diffusion velocity are equal
Lower than graphite, this will limit performance of silicon under the conditions of high current is high-power.
Due to the above problem, part attention is transferred on the sub- silicon of oxidation by academia and industrial circle.Compared with nano-silicon,
It aoxidizes sub- silicon and although sacrifices portion capacity, but its expansion by-product oxygen that is relatively small, and generating in charge and discharge process
Buffer function can be provided by changing lithium, lithium metasilicate, lithium metasilicate etc., greatly improve the cycle performance of material.But material is led
Electrically relatively poor, head effect is lower.
Summary of the invention
In view of the above deficiencies, the present invention provides a kind of Silicon-rich SiOxThe preparation method of C-material, comprehensive Si's and SiO is excellent
Disadvantage becomes SiO by the group that etching SiO disproportionated reaction generates using SiO as raw material2The SiO of@SiO@Six, obtain porous
Then silica-base material passes through CVD（Chemical vapor deposition）Method deposits Si in the pore structure of porous silicon-base material, to obtain richness
The SiO of siliconxMaterial, by then passing through the silicon of disproportionated reaction generation and the silicon of CVD deposition, therefore silicon crystal grain is smaller, and partial size is about
Furthermore the electronic conductivity of material can be improved in 3nm ~ 20nm by the carbon coating layer that CVD deposition is formed.System through the invention
The Silicon-rich SiO of Preparation Method preparationxThe gram volume of C-material and for the first time coulombic efficiency are above commercialized SiO, cyclical stability
Relatively preferably, it overcomes SiO material head and imitates lower defect.
To achieve the goals above, the present invention uses following technical scheme：
A kind of Silicon-rich SiOxThe preparation method of C-material, includes the following steps：
A, SiO is placed in disproportionated reaction in inert atmosphere and obtains group as SiO2The SiO of@SiO@Six；
B, by the SiO in step axPorous silicon-base material is made after etching；
C, silicon source gas is added, silicon is deposited in the inside of the porous silicon-base material by chemical vapour deposition technique, obtains Silicon-rich
SiOxMaterial；Here the reaction unit of chemical vapour deposition technique is not specifically limited, preferably rotary furnace, and the present invention is having
Rotary furnace is all made of in body embodiment;
D, the silicon source gas is changed to carbon-source gas and passes through chemical vapour deposition technique again in the Silicon-rich SiOxThe hole of material
Structure and surface form carbon coating layer, and Silicon-rich SiO is madexC-material;
Asia silicon SiO is aoxidized due to its poorly conductive, it is first to imitate low, therefore limit it in the extensive use of field of lithium ion battery,
The present invention passes through the SiO of etching SiO disproportionated reaction generation using SiO as raw materialxPorous silicon-base material is made, then passes through CVD
Method deposits silicon in the inside of porous silicon-base material, obtains the SiO of Silicon-richxMaterial, due to the Si by being generated after disproportionated reaction, again
The Si deposited by CVD method, obtained silicon crystal grain partial size is smaller, about 3nm ~ 20nm, so that the volume of material is swollen
It is swollen smaller, greatly improve the cycle performance of material；Further by CVD method in Silicon-rich SiOxMaterial internal and surface are equal
Even deposition carbon coating layer, can be improved the electronic conductivity of material.Therefore, the Silicon-rich SiO prepared through the inventionxC-material gram
The shortcomings that having taken commercialization SiO material improves the capacity and coulombic efficiency for the first time of material.
In addition, preparation method provided by the invention, processing step is simple, only due to chemical vapor deposited silicon and carbon material
Gas source is needed replacing, does not need that cooling discharge after deposition silicon, mixed carbon source, heat up carbonization again, therefore is easily controllable and realize and advise greatly
Mould production.
Further, in step a, the inert atmosphere is one or more of nitrogen, argon gas, helium, neon；
Its temperature of the disproportionated reaction is 900 DEG C ~ 1200 DEG C, and the reaction time is 2h ~ 12h, has suitable silicon wafer to obtain in structure
The SiO of grain partial sizexMaterial.
Further, in stepb, the technique of the etching is to be etched using HF solution, KOH solution or NaOH solution,
To remove the SiO of disproportionated reaction generation2, the irreversible capacity loss of material is reduced, is then filtered, washed, is dried in vacuo,
In, the vacuum drying temperature is 80 DEG C ~ 100 DEG C, and vacuum degree is -0.8MPa ~ -1MPa.
Preferably, the etching uses HF solution, wherein the mass fraction of the HF solution is 35% ~ 44%, the SiOx
Mass ratio with HF solution is 2:1~1:2, the time of the etching is 0.5h ~ 2h；
Further, in step c, the silicon source gas is one of silane, dichlorosilane, trichlorosilane, tetrachloro silicane
Or it is several, flow velocity is 1mL/min ~ 4mL/min；The chemical vapor deposition, depositing temperature are 600 DEG C ~ 1000 DEG C, when deposition
Between be 2h ~ 12h.
Further, in step d, the carbon-source gas be methane or its homologue, acetylene or its homologue, toluene or
One or more of its homologue, ethyl alcohol or its homologue, flow velocity are 1mL/min ~ 4mL/min；The chemical vapor deposition
Method, depositing temperature are 700 DEG C ~ 1000 DEG C, and sedimentation time is 2h ~ 12h.
Further, in step d, the carbon of the carbon coating layer formed with a thickness of 10nm ~ 100nm, chemical gas-phase method
Clad dense uniform improves the electronic conductivity of material, furthermore the blocked up specific discharge capacity that will lead to material of carbon coating layer
The advantages of reducing, losing silica-base material high capacity；Carbon coating layer is excessively thin, will lead to material cladding it is uneven or not perfect, in turn
The coulombic efficiency and cycle performance for leading to material reduce, and therefore, preferably carbon coating layer is in the present invention with a thickness of 10nm ~ 100nm.
Further, in the Silicon-rich SiOxIn C-material, 0 < x < 1, the Silicon-rich SiOxSilicon crystal grain partial size in C-material
For 3nm ~ 20nm.Silicon crystal grain partial size produced by the present invention is 3nm ~ 20nm, this is because when partial size is larger, with the depth of embedding lithium
Entering, particle internal stress distribution unevenly causes crackle to generate, and cause silicon crystal grain and conductive network to be in electrical contact and loses, the internal resistance of cell
Increase；And the lesser silicon crystal grain of partial size is due to large specific surface area, big with the contact area of conductive network in the electrodes, lithium deintercalation
Bulk effect in journey influences electrochemistry cycle performance that is smaller, therefore being conducive to electrode on it
It is another object of the present invention to provide a kind of Silicon-rich SiOxC-material.
Third object of the present invention is to provide Silicon-rich SiOxC-material is in the application being used to prepare in lithium ion battery.
By Silicon-rich SiO of the inventionxC-material prepares lithium ion battery as negative electrode material, carries out electrification to lithium ion battery obtained
The test of performance is learned, the specific capacity and cyclical stability of lithium ion battery obtained are improved.
Detailed description of the invention
Fig. 1 is Silicon-rich SiO prepared by embodiment 1xThe SEM of C-material schemes；
Fig. 2 is Silicon-rich SiO prepared by embodiment 1xThe EDS of C-material schemes；
Fig. 3 is Silicon-rich SiO prepared by embodiment 1xThe local T EM of C-material schemes；
Fig. 4 is Silicon-rich SiO prepared by embodiment 1xThe TEM of C-material schemes；
Fig. 5 is the Silicon-rich SiO in embodiment 1 and comparative examplexHead of the button cell of C-material assembling under 0.1C current density
Secondary charging and discharging curve.
Specific embodiment
To facilitate the understanding of the present invention, technical solution of the present invention is done with reference to the accompanying drawings and examples further clear
Chu, complete explanation, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
It should know, the various reagents used, raw material are commodity commercially or can in the present invention
With the product as made from well known method.
Embodiment 1
10g SiO is placed in porcelain boat, is subsequently placed in the tube furnace in argon atmosphere, with the heating rate of 5 DEG C/min
Tube furnace is warming up to 900 DEG C, keeps the temperature 2h, SiO obtained is taken out after coolingx.By SiOxThe HF for being 40% with mass fraction is water-soluble
Liquid in mass ratio 2:1 mixing, impregnates 0.5h, then filters, and makes to be washed with deionized 3 times and is in neutrality to cleaning solution, then sets
In the vacuum oven that vacuum degree is -0.8MPa, dry obtained porous silicon-base material at 80 DEG C.5g porous silicon-base material is taken to set
In CVD furnace, the air being passed through in argon gas discharge CVD furnace is subsequently passed silane gas, gas flow 4mL/min, with 5 DEG C/
Tube furnace is warming up to 600 DEG C by the heating rate of min, keeps the temperature 2h, and stopping is passed through silane, then tube furnace is warming up to 800 DEG C, leads to
Enter acetylene gas, gas flow 4mL/min keeps the temperature 2h at 800 DEG C, and stopping is passed through acetylene gas, and after cooling, Silicon-rich is made
SiOxC-material, wherein Silicon-rich SiOxThe silicon crystal grain partial size of C-material is 3nm ~ 20nm, and carbon coating layer is with a thickness of 10nm ~ 100nm.
Embodiment 2
10g SiO is placed in porcelain boat, is subsequently placed in the tube furnace in nitrogen protection atmosphere, with the heating rate of 5 DEG C/min
Tube furnace is warming up to 900 DEG C, keeps the temperature 12h, SiO obtained is taken out after coolingx.By SiOxThe HF for being 35% with mass fraction is water-soluble
Liquid in mass ratio 1:2 mixing, impregnate 2h, then filter, and make to be washed with deionized 3 times and are in neutrality to cleaning solution, are subsequently placed in
Vacuum degree is dry obtained porous silicon-base material at 80 DEG C in the vacuum oven of -1MPa.5g porous silicon-base material is taken to be placed in
In CVD furnace, the air being passed through in nitrogen discharge CVD furnace is subsequently passed silane gas, gas flow 1mL/min, with 5 DEG C/
Tube furnace is warming up to 600 DEG C by the heating rate of min, keeps the temperature 12h, and stopping is passed through silane gas, tube furnace is warming up to 700
DEG C, it is passed through acetylene gas, gas flow 1mL/min keeps the temperature 12h at 700 DEG C, and stopping is passed through acetylene gas, after cooling, is made
Silicon-rich SiOxC-material, wherein Silicon-rich SiOxThe silicon crystal grain partial size of C-material be 3nm ~ 20nm, carbon coating layer with a thickness of 10nm ~
100nm。
Embodiment 3
10g SiO is placed in porcelain boat, is subsequently placed in the tube furnace in nitrogen protection atmosphere, with the heating rate of 5 DEG C/min
Tube furnace is warming up to 1200 DEG C, keeps the temperature 2h, SiO obtained is taken out after coolingx.By SiOxThe HF for being 44% with mass fraction is water-soluble
Liquid in mass ratio 2:1 mixing, impregnates 0.5h, then filters, and makes to be washed with deionized 3 times and is in neutrality to cleaning solution, then sets
In the vacuum oven that vacuum degree is -0.8MPa, dry obtained porous silicon-base material at 100 DEG C.Take 5g porous silicon-base material
It is placed in CVD furnace, the air being passed through in nitrogen discharge CVD furnace is subsequently passed dichlorosilane and silane mixture gas, gas flow
For 4mL/min, tube furnace is warming up to 1000 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 2h, stopping is passed through dichlorosilane and silicon
Alkane mixed gas keeps tube furnace to 1000 DEG C, is passed through methane gas, gas flow 4mL/min, keeps the temperature at 1000 DEG C
2h, stopping is passed through methane gas, and after cooling, Silicon-rich SiO is madexC-material, wherein Silicon-rich SiOxThe silicon crystal grain partial size of C-material
For 3nm ~ 20nm, carbon coating layer is with a thickness of 10nm ~ 100nm.
Embodiment 4
10g SiO is placed in porcelain boat, is subsequently placed in the tube furnace in helium protective atmosphere, with the heating rate of 5 DEG C/min
Tube furnace is warming up to 1100 DEG C, keeps the temperature 8h, SiO obtained is taken out after coolingx.By SiOxThe HF for being 40% with mass fraction is water-soluble
Liquid in mass ratio 1:1 mixing, impregnates 1.5h, then filters, and makes to be washed with deionized 3 times and is in neutrality to cleaning solution, then sets
In the vacuum oven that vacuum degree is -1MPa, dry obtained porous silicon-base material at 90 DEG C.5g porous silicon-base material is taken to be placed in
In CVD furnace, the air being passed through in helium discharge CVD furnace is subsequently passed trichlorosilane gas, gas flow 2.5mL/min, with
Tube furnace is warming up to 800 DEG C by the heating rate of 5 DEG C/min, keeps the temperature 8h, and stopping is passed through trichlorosilane gas, tube furnace is kept
To 800 DEG C, it is passed through toluene gas, gas flow 2.5mL/min keeps the temperature 8h at 800 DEG C, and stopping is passed through toluene gas, cools down
Afterwards, Silicon-rich SiO is madexC-material, wherein Silicon-rich SiOxThe silicon crystal grain partial size of C-material be 3nm ~ 20nm, carbon coating layer with a thickness of
10nm~100nm。
Embodiment 5
10g SiO is placed in porcelain boat, is subsequently placed in the tube furnace in nitrogen protection atmosphere, with the heating rate of 5 DEG C/min
Tube furnace is warming up to 1200 DEG C, keeps the temperature 2h, SiO obtained is taken out after coolingx.By SiOxIn KOH aqueous solution, 1.5h is impregnated,
Then it filters, makes to be washed with deionized 3 times and be in neutrality to cleaning solution, be subsequently placed in the vacuum oven that vacuum degree is -1MPa
In, dry obtained porous silicon-base material at 80 DEG C.It takes 5g porous silicon-base material to be placed in CVD furnace, is passed through in nitrogen discharge CVD furnace
Air, be subsequently passed silane gas, tube furnace is warming up to by gas flow 4mL/min with the heating rate of 5 DEG C/min
600 DEG C, 2h is kept the temperature, stopping is passed through silane gas, tube furnace is warming up to 1000 DEG C, is passed through acetylene gas, gas flow is
4mL/min keeps the temperature 2h at 1000 DEG C, and stopping is passed through acetylene gas, is cooled to room temperature discharging, Silicon-rich SiO is madexC-material,
In, Silicon-rich SiOxThe silicon crystal grain partial size of C-material is 3nm ~ 20nm, and carbon coating layer is with a thickness of 10nm ~ 100nm.
Embodiment 6
10g SiO is placed in porcelain boat, is subsequently placed in the tube furnace in nitrogen protection atmosphere, with the heating rate of 5 DEG C/min
Tube furnace is warming up to 1200 DEG C, keeps the temperature 2h, SiO obtained is taken out after coolingx.By SiOxIn NaOH aqueous solution, impregnate
Then 1.5h is filtered, make to be washed with deionized 3 times and be in neutrality to cleaning solution, and it is dry to be subsequently placed in the vacuum that vacuum degree is -1MPa
In dry case, dry obtained porous silicon-base material at 80 DEG C.It takes 5g porous silicon-base material to be placed in CVD furnace, is passed through nitrogen discharge CVD
Air in furnace, is subsequently passed tetrachloro silicane gas, gas flow 4mL/min, with the heating rate of 5 DEG C/min by tube furnace
600 DEG C are warming up to, 2h is kept the temperature, stopping is passed through tetrachloro silicane gas, tube furnace is warming up to 1000 DEG C, is passed through alcohol gas, gas
Body flow is 4mL/min, and 2h is kept the temperature at 1000 DEG C, and stopping is passed through alcohol gas, is cooled to room temperature discharging, Silicon-rich SiO is madex-C
Material, wherein Silicon-rich SiOxThe silicon crystal grain partial size of C-material is 3nm ~ 20nm, and carbon coating layer is with a thickness of 10nm ~ 100nm.
Comparative example
The untreated SiO of 5g is taken to be placed in CVD furnace, the air being passed through in argon gas discharge CVD furnace is passed through acetylene gas, gas
Flow is 4mL/min, CVD furnace is risen to 800 DEG C according to the heating rate of 5 DEG C/min, and keep the temperature 2h, and stopping is passed through acetylene gas
Body after cooling, can be obtained carbon-coated SiO material.
Silicon-rich SiO prepared by embodiment 1xC-material carries out material characterization, as a result as shown in Fig. 1 ~ 4.Fig. 1 is Silicon-rich
SiOxThe SEM of C-material schemes, and can observe and know that the pattern for preparing material and SiO raw material are substantially similar, is in bulk morphologies.Fig. 2
For Silicon-rich SiOxThe EDS of C-material schemes, it can be found that there are mainly three types of Elemental redistributions, respectively Si, O, C for material, wherein O is main
From raw material SiO, carbon material is distributed in the surface of Si, and is distributed comparatively uniform.Fig. 3 is Silicon-rich SiOxC-material
Local T EM figure, can observe and know occur the lattice fringe of Si in material after high temperature, wherein D (111) spacing of lattice is
3.183, the silicon crystal grain partial size of generation shows that the Si of SiO high-temperature part disproportionation and CVD deposition is crystalline silicon in 20nm or so.
Fig. 4 is Silicon-rich SiOxThe TEM of C-material schemes, and after CVD deposition, carbon is uniformly coated on SiOxSurface, coating thickness is about
20nm。
The Silicon-rich SiO that will be prepared in embodiment 1xC-material, conductive agent SP and binder LA133 are according to mass ratio 8:1:1
Conjunction slurry, coating are carried out, CR2016 button cell is assembled into, wherein electrolyte uses 1mol/L LiPF6Ethylene carbonate（EC）
+ dimethyl carbonate（DMC）Solution, and electrochemical property test is carried out, as a result as shown in Figure 5.Under 0.1C current density, material
First discharge specific capacity be 2305.6mAh/g, charge specific capacity 1851.7mAh/g, for the first time coulombic efficiency be 80.3%.
The carbon-coated SiO material prepared in comparative example is assembled into CR2016 button according to method similarly to Example 1
Formula battery, and electrochemical property test is carried out, as a result as shown in Figure 5.Under 0.1C current density, the electric discharge specific volume for the first time of material
Amount is 2210.9mAh/g, charge specific capacity 1647.2mAh/g, and coulombic efficiency is 74.5% for the first time.
By embodiment 1 and comparative example it can be found that Silicon-rich SiO prepared by the present inventionxMaterial not only can be improved in C-material
The initial charge specific capacity of material also improves the coulombic efficiency for the first time of material, this is just because of by part SiO in SiO matrix2It carves
The reason of losing and filling Si, and the Si of the Si of SiO disproportionated reaction generation and CVD deposition（It is limited to the SiO that disproportionation generates2's
Granular size）Partial size is 3nm ~ 20nm, and volume expansion is relatively small, around there is the buffering expansion of SiO matrix, therefore the first effect of material
And cycle performance gets a promotion, in addition, the carbon coating layer dense uniform of CVD deposition, not only improves the electronic conductivity of material,
The cyclical stability of material is improved to a certain extent.
The above, only preferred embodiments of the present invention, but scope of protection of the present invention is not limited thereto, it is any ripe
Know those skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its invention structure
Think of is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of Silicon-rich SiOxThe preparation method of C-material, it is characterised in that：Include the following steps：
A, SiO is placed in disproportionated reaction in inert gas and obtains group as SiO2The SiO of@SiO@Six；
B, by the SiO in step axPorous silicon-base material is made after etching；
C, silicon source gas is added, silicon is deposited in the inside of the porous silicon-base material by chemical vapour deposition technique, obtains Silicon-rich
SiOxMaterial；
D, the silicon source gas is changed to carbon-source gas and passes through chemical vapour deposition technique again in the Silicon-rich SiOxIt ties in the hole of material
Structure and surface form carbon coating layer, and Silicon-rich SiO is madexC-material.
2. preparation method as described in claim 1, it is characterised in that：In step a, the inert gas is nitrogen, argon
One or more of gas, helium, neon；
Its temperature of the disproportionated reaction is 900 DEG C ~ 1200 DEG C, and the reaction time is 2h ~ 12h.
3. preparation method as described in claim 1, it is characterised in that：In stepb, the technique of the etching is molten using HF
It after liquid, KOH solution or NaOH solution etching, is filtered, washed, is dried in vacuo, wherein the vacuum drying temperature is 80 DEG C
~ 100 DEG C, vacuum degree is -0.8MPa ~ -1MPa.
4. preparation method as claimed in claim 3, it is characterised in that：The etching uses HF solution, wherein the HF solution
Mass fraction be 35% ~ 44%, the SiOxMass ratio with HF solution is 2:1~1:2, time of the etching be 0.5h ~
2h。
5. preparation method as described in claim 1, it is characterised in that：In step c, the silicon source gas is silane, dichloro
One or more of silane, trichlorosilane, tetrachloro silicane, flow velocity are 1mL/min ~ 4mL/min；The chemical vapor deposition
Method, depositing temperature are 600 DEG C ~ 1000 DEG C, and sedimentation time is 2h ~ 12h.
6. preparation method as described in claim 1, it is characterised in that：In step d, the carbon-source gas is methane or it is same
It is one or more of object, acetylene or its homologue, toluene or its homologue, ethyl alcohol or its homologue, flow velocity 1mL/min
~4mL/min；The chemical vapour deposition technique, depositing temperature are 700 DEG C ~ 1000 DEG C, and sedimentation time is 2h ~ 12h.
7. preparation method as described in claim 1, it is characterised in that：In step d, the carbon coating layer with a thickness of 10nm
~100nm。
8. preparation method as described in claim 1, it is characterised in that：In the Silicon-rich SiOxIn C-material, 0 < x < 1 is described
Silicon-rich SiOxSilicon crystal grain partial size is 3nm ~ 20nm in C-material.
9. one kind Silicon-rich SiO as made from the described in any item preparation methods of claim 1 ~ 8xC-material.
10. Silicon-rich SiO as claimed in claim 9xC-material is in the application being used to prepare in lithium ion battery.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111342020A (en) * | 2020-03-11 | 2020-06-26 | 中国科学院宁波材料技术与工程研究所 | Silicon-based negative electrode material, preparation method thereof and lithium ion battery |
| CN111384380A (en) * | 2018-12-29 | 2020-07-07 | 上海杉杉科技有限公司 | Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery prepared from silicon-carbon negative electrode material |
| CN113782740A (en) * | 2020-06-10 | 2021-12-10 | 恒大新能源技术(深圳)有限公司 | Silicon/lithium silicate composite material, preparation method thereof and power battery |
| CN114050251A (en) * | 2021-11-18 | 2022-02-15 | 兰州城市学院 | Preparation and application of silicon-carbon composite micro-nano structure material |
| CN114784253A (en) * | 2022-05-20 | 2022-07-22 | 电子科技大学 | Silicon-carbon oxide composite negative electrode material for secondary battery and preparation and application thereof |
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| CN111384380A (en) * | 2018-12-29 | 2020-07-07 | 上海杉杉科技有限公司 | Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery prepared from silicon-carbon negative electrode material |
| CN111384380B (en) * | 2018-12-29 | 2022-02-01 | 上海杉杉科技有限公司 | Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery prepared from silicon-carbon negative electrode material |
| CN111342020A (en) * | 2020-03-11 | 2020-06-26 | 中国科学院宁波材料技术与工程研究所 | Silicon-based negative electrode material, preparation method thereof and lithium ion battery |
| CN113782740A (en) * | 2020-06-10 | 2021-12-10 | 恒大新能源技术(深圳)有限公司 | Silicon/lithium silicate composite material, preparation method thereof and power battery |
| CN114050251A (en) * | 2021-11-18 | 2022-02-15 | 兰州城市学院 | Preparation and application of silicon-carbon composite micro-nano structure material |
| CN114050251B (en) * | 2021-11-18 | 2024-01-19 | 兰州城市学院 | Preparation and application of silicon-carbon composite micro-nano structure material |
| CN114784253A (en) * | 2022-05-20 | 2022-07-22 | 电子科技大学 | Silicon-carbon oxide composite negative electrode material for secondary battery and preparation and application thereof |
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