CN108183198A - A kind of lithium ion battery negative material and its preparation and application - Google Patents
A kind of lithium ion battery negative material and its preparation and application Download PDFInfo
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Abstract
The present invention provides a kind of lithium ion battery negative material and its preparation and application, and the material is the material of carbon nanometer layer coated Si, and the material has the three-dimensional cross-linked aerogel structure of carbon nanometer layer, and the silicon nano of cladding is distributed in carbon nanometer layer；Contain N element in the carbon nanometer layer, while also containing one or more of heterogeneous element P, S, B.Preparation method includes the nano-silicon of the surface modification and preparation of amino-compound dispersion liquid, the preparation of the carbon-silicon composite material and preparation of carbon nanometer layer cladding silicon materials.Clad structure greatly reduces the volume expansion of silicon；The gel structure of high porosity, which effectively alleviates silicon expansion, influences electrode structure；And three-dimensional cross-linked carbon nanometer layer provides preferable conductive network.Method for coating of the present invention is easy, and raw material sources are extensive, cheap, and process conditions are easy to control, and operating cost is low, great industrial prospect.Compared to existing method for coating, have many advantages, such as that clad is uniform, cladding rate is fast.
Description
Technical field
The present invention relates to lithium ion battery negative material and its preparing technical fields, and in particular to a kind of carbon nanometer layer cladding
Silicium cathode material and preparation method thereof.
Background technology
Lithium ion battery as a kind of using very extensive energy storage device, has energy density height, self discharge
Small, the advantages that operating voltage range is wide, memory-less effect, service life are long, non-environmental-pollution, performance of lithium ion battery it is final
Deciding factor is electrode material, and wherein negative material plays a crucial role the raising of performance of lithium ion battery.Mesh
The application of preceding negative material is difficult mainly based on conventional graphite material, but graphite specific capacity is close to the theoretical value of 372mAh/g
Have the space of promotion, can not meet the needs of high-energy-density dynamic lithium battery, thus develop other novel anode materials so as to
Promoting lithium battery performance has become negative material research field hot spot.
The theoretical specific capacity of silicon is 4200mAh/g, and the voltage platform far above the specific capacity of graphite material, and silicon is slightly above
Graphite will not cause surface to analyse lithium in charging, and security performance is more preferable, and in addition silicon derives from a wealth of sources, and storage is abundant, so silicon quilt
Think most possibly to substitute one of novel anode material of graphite.But using silicon as lithium ion battery negative material in the mistake of embedding lithium
Embedded abjection of the volume expansion up to lithium ion in 300%. charge and discharge process repeatedly, the gradual dusting of material cause structure to collapse in journey
It collapses, eventually leads to electrode active material and be detached from collector, lose electrical contact, cycle performance of battery is caused to substantially reduce；In addition,
Due to this bulk effect, silicon is difficult to form stable solid electrolyte interface (SEI) film in the electrolytic solution；Along with electrode knot
The destruction of structure constantly forms new SEI films in the silicon face exposed, exacerbates corrosion and the capacity attenuation of silicon.
The methods of mainly using surface modification for the modification of high power capacity silicium cathode material at present, adulterating, is compound, which is formed, wraps
It covers or the system of high degree of dispersion, by improving the mechanical property of material, to alleviate in volume expansion during removal lithium embedded generates
Destruction of the stress to material structure, so as to improve its electrochemical cycle stability.Though these materials can obtain one in cyclicity
Fixed improvement, but effect is still not ideal enough, can not meet the performance requirement of high-performance power lithium-ion battery.
Invention content
The present invention in view of the deficiencies of the prior art, has invented a kind of carbon nanometer layer cladding silicon materials, has effectively solved silicon
During as lithium ion battery negative material the problem of volume expansion, the special capacity fade speed of carbon silicium cathode material can be substantially reduced
Degree, the invention also provides a kind of preparation methods for preparing carbon nanometer layer cladding silicon materials.The present invention is using scheme in detail below
It realizes：
A kind of lithium ion battery negative material, the material are the material of carbon nanometer layer coated Si, and the material has carbon
Nanometer layer is cross-linked with each other into three dimensional skeletal structure, and silicon nano is distributed in carbon nanometer layer.
The carbon nanometer layer is porous carbon nanosheet layer, and the lamellar spacing of the carbon nanometer layer is 10-300nm, porous
The length and width of carbon nanosheet layer be respectively 20nm-5 μm, porosity 0.5-2cm3/ g, aperture size is in 0.5nm-
In the range of 20nm；The grain size of silicon nano is 10-100nm.
Contain N element in the carbon nanometer layer, while also containing one or more of heterogeneous element P, S, B；Institute
The mass content for stating N element in carbon nanometer layer is the total of one or more of 1%-10%, described heterogeneous element P, S, B
Mass content be 1%-10%.
The preparation method of the lithium ion battery negative material, it is characterised in that：Include the following steps,
(1) preparation of the nano-silicon of surface modification and amino-compound dispersion liquid：Disperse in absolute ethyl alcohol at through surface
The nano-silicon powder of reason, heating water bath while, add in coupling agent, constant temperature stirring 8-16h postcooling filtration dryings in dispersion liquid
Obtain the nano-silicon of surface modification；Gained nano-silicon and amino-compound are disperseed in a solvent.
(2) preparation of carbon-silicon composite material：Polyalcohol and inorganic acid are uniformly mixed makes it after heated under vacuum
Esterification occurs, the amino chemical combination added with the nano-silicon of surface modification obtained by step (1) is added in esterification reaction product
The dispersion liquid of object, again heating bring it about salt-forming reaction, obtain carbon-silicon composite material；
(3) preparation of carbon nanometer layer cladding silicon materials：By carbon-silicon composite material obtained by step (2) in inert atmosphere high temperature
Carbonization treatment obtains carbon nanometer layer cladding silicon materials.
Nano-silicon powder surface treatment method described in step (1) is the Xiang Shuan under conditions of ice-water bath or -4 DEG C to 4 DEG C
The concentrated sulfuric acid is added in oxygen water, adds in simple substance nano-silicon powder after mixing, again washed, dry surface after mixing
Nano-silicon powder that treated.
The mass fraction of hydrogen peroxide described in step (1) is 25%-35%, and the mass fraction of the concentrated sulfuric acid is 90-98%；It is dense
The volume ratio of sulfuric acid and hydrogen peroxide is 5:1-10:1, the addition of simple substance silicon nanoparticle is the 5-20mg/mL concentrated sulfuric acids.
Step (1) described coupling agent is one in Silane coupling agent KH550, silane coupling agent 902, silane coupling agent 910
Kind is two or more；Mass concentration of the nano-silicon powder in absolute ethyl alcohol dispersion liquid is 0.2-3mg/mL；The coupling added in
The volume ratio of agent and absolute ethyl alcohol is 1：20-1：80；The temperature of heating water bath is 50-80 DEG C.
Step (1) described amino-compound is urea, one or more kinds of in melamine, cyanamide, amino acid；It is described
Solvent in the dispersion liquid of amino-compound is water, mixed liquor one or more kinds of in methanol, ethyl alcohol, ethylene glycol；It is described
Mass concentration of the amino-compound in the dispersion liquid of the nano-silicon of surface modification is 2-6mg/mL.The nanometer of the surface modification
Mass concentration of the silicon in dispersion liquid is 1-10mg/mL；Polyalcohol described in step (2) is pentaerythrite, xylitol, sorbierite
Middle one or more；The inorganic acid is mass concentration 20-90% boric acid, mass concentration 20-85% phosphoric acid, mass concentration
It is one or more kinds of in 20-98% sulfuric acid, mass concentration 20-80% nitric acid；Polyalcohol and inorganic acid in the step (1)
The ratio of the amount of substance is 2：1-1：8；The amino-compound and the ratio of the amount of the substance of inorganic acid before esterification are 5：1-1：
5；
The condition of esterification described in step (2) is reacts 0.5-5h, vacuum degree 0.03- at 70-200 DEG C
0.2Mpa；The salt-forming reaction condition reacts 2-24h at a temperature of being 30-150 DEG C；Carbonization treatment condition is described in step (3)
In from room temperature to keeping 0.5-3h under the conditions of 300-600 DEG C, raising temperature is to 700-1100 DEG C, heating rate 2-10
DEG C/min, this temperature 0.5-3h is kept, is cooled to room temperature；Inert atmosphere described in step (3) for nitrogen, argon gas or nitrogen and
The gaseous mixture of argon gas.
The carbon silicon covering material can be used as lithium ion battery negative material.
Compared with prior art, the carbon silicium cathode material that prepared by the present invention is three-dimensional cross-linked aerogel structure, cladding
Silicon nano is distributed in carbon-coating surface.Clad structure greatly reduces the volume expansion of silicon；The gel structure of high porosity
It is effective to alleviate silicon expansion to electrode structure influence；And three-dimensional cross-linked carbon nanometer layer provides preferable conductive network.
Due to the protection of carbon aerogels clad, silicon materials gradually participate in electrochemical reaction in cyclic process, and cyclicity significantly changes
It is kind.And the method for the present invention is easy, and operating cost is low, great industrial prospect.
Description of the drawings
Fig. 1 is carbon nanometer layer coated Si material structure schematic diagram.
Specific embodiment
Embodiment 1
The nano-silicon of surface modification and the preparation of amino-compound dispersion liquid：Under conditions of ice-water bath, to 40mL dioxygens
The 10mL concentrated sulfuric acids are added in water, are stirred evenly, then add in 0.4g simple substance silicon nanoparticle (10nm), continue to stir 8h, centrifugation
Washing obtains processed silicon nanoparticle after dry；The processed silicon nanoparticles of 0.3g is taken to be added to 100mL absolute ethyl alcohols
In, 1mLKH550 is slowly added dropwise in ultrasonic disperse 30min, 70 DEG C of stirrings of water-bath, and constant temperature stirring 12h is cooled down, filtered, made after dry
The silicon nanoparticle of KH550 surface modifications is obtained, weighs the silicon nanoparticle 250mg of surface modification in round-bottomed flask, is added in
120mL ethyl alcohol and 16.38g melamines, are sufficiently stirred 1.5h,
The preparation of carbon-silicon composite material：6.8g pentaerythrites are weighed in flask, add in 29.40g phosphoric acid, vacuum distillation
(vacuum degree 0.1MPa), stirring are heated to 120 DEG C, keep the temperature 1.5h, obtain the thick pentaerythritol phosphate of pale yellow transparent
Liquid.The nano-silicon of the surface modification obtained in upper step and amino-compound dispersion liquid are poured into equipped with wherein, are heated to 80 DEG C,
6h is stirred at reflux, obtains white emulsion, the big white solid of rotary evaporation.
Carbon nanometer layer coats the preparation of silicon materials：By white solid, quartz boat is put in, under nitrogen atmosphere, 5 DEG C/min's
Heating rate is warming up to 350 DEG C, keeps 0.5h, continues to be warming up to 900 DEG C with the heating rate of 5 DEG C/min, keeps 2h, be cooled to
Room temperature is taken out.
There is resulting materials carbon nanometer layer to be cross-linked with each other into three dimensional skeletal structure, and silicon nano is distributed in carbon nanometer layer
In.Carbon nanometer layer is porous carbon nanosheet layer, and the lamellar spacing of carbon nanometer layer is 20-50nm, porous carbon nanosheet layer
Length and width is respectively 20nm-5 μm, porosity 1.5-1.8cm3/ g, aperture size is in the range of 0.5nm-8nm；Silicon is received
The grain size of rice corpuscles is 10nm..Contain N element in carbon nanometer layer, the mass content of N element is 2%-5%, while also containing different
Prime element P accounts for total mass content as 2%-5%.As ion cathode material lithium, 0.1C discharge capacities are about 1500mAh/ for the first time
G, coulombic efficiency 75%, the 20th time cycle when material discharge capacitance maintain 70%.
Embodiment 2
The nano-silicon of surface modification and the preparation of amino-compound dispersion liquid：Under conditions of ice-water bath, to 40mL dioxygens
The 10mL concentrated sulfuric acids are added in water, are stirred evenly, then add in 0.4g simple substance nano-silicon (30nm) particle, continue to stir 8h, centrifugation
Washing obtains processed silicon nanoparticle after dry；The processed silicon nanoparticles of 0.3g is taken to be added to 100mL absolute ethyl alcohols
In, 1mLKH550 is slowly added dropwise in ultrasonic disperse 30min, 70 DEG C of stirrings of water-bath, and constant temperature stirring 12h is cooled down, filtered, made after dry
The silicon nanoparticle of KH550 surface modifications is obtained, weighs the silicon nanoparticle 250mg of surface modification in round-bottomed flask, is added in
120mL ethyl alcohol and 8.19g melamines, are sufficiently stirred 1.5h,
The preparation of carbon-silicon composite material：6.8g pentaerythrites are weighed in flask, add in 29.40g phosphoric acid, vacuum distillation
(vacuum degree 0.1MPa), stirring are heated to 120 DEG C, keep the temperature 1.5h, obtain the thick pentaerythritol phosphate of pale yellow transparent
Liquid.The nano-silicon of the surface modification obtained in upper step and amino-compound dispersion liquid are poured into equipped with wherein, are heated to 80 DEG C,
6h is stirred at reflux, obtains white emulsion, the big white solid of rotary evaporation.
Carbon nanometer layer coats the preparation of silicon materials：By white solid, quartz boat is put in, under nitrogen atmosphere, 5 DEG C/min's
Heating rate is warming up to 350 DEG C, keeps 0.5h, continues to be warming up to 950 DEG C with the heating rate of 5 DEG C/min, keeps 4h, be cooled to
Room temperature is taken out.
There is resulting materials carbon nanometer layer to be cross-linked with each other into three dimensional skeletal structure, and silicon nano is distributed in carbon nanometer layer
In.Carbon nanometer layer is porous carbon nanosheet layer, and the lamellar spacing of carbon nanometer layer is 50-80nm, porous carbon nanosheet layer
Length and width is respectively 20nm-5 μm, porosity 1.3-1.5cm3/ g, aperture size is in the range of 0.5nm-8nm；Silicon is received
The grain size of rice corpuscles is 30nm..Contain N element in carbon nanometer layer, the mass content of N element is 2%-5%, while also containing different
Prime element P accounts for total mass content as 2%-5%.
Embodiment 3
The nano-silicon of surface modification and the preparation of amino-compound dispersion liquid：Under conditions of ice-water bath, to 40mL dioxygens
The 10mL concentrated sulfuric acids are added in water, are stirred evenly, then add in 0.4g simple substance silicon nanoparticle (50nm), continue to stir 8h, centrifugation
Washing obtains processed silicon nanoparticle after dry；The processed silicon nanoparticles of 0.3g is taken to be added to 100mL absolute ethyl alcohols
In, 1mLKH550 is slowly added dropwise in ultrasonic disperse 30min, 70 DEG C of stirrings of water-bath, and constant temperature stirring 12h is cooled down, filtered, made after dry
The silicon nanoparticle of KH550 surface modifications is obtained, weighs the silicon nanoparticle 250mg of surface modification in round-bottomed flask, is added in
120mL ethyl alcohol and 8.19g melamines, are sufficiently stirred 1.5h,
The preparation of carbon-silicon composite material：13.6g pentaerythrites are weighed in flask, add in 29.40g phosphoric acid, vacuum distillation
(vacuum degree 0.1MPa), stirring are heated to 120 DEG C, keep the temperature 1.5h, obtain the thick pentaerythritol phosphate of pale yellow transparent
Liquid.The nano-silicon of the surface modification obtained in upper step and amino-compound dispersion liquid are poured into equipped with wherein, are heated to 80 DEG C,
6h is stirred at reflux, obtains white emulsion, the big white solid of rotary evaporation.
Carbon nanometer layer coats the preparation of silicon materials：By white solid, quartz boat is put in, under nitrogen atmosphere, 5 DEG C/min's
Heating rate is warming up to 350 DEG C, keeps 0.5h, continues to be warming up to 1050 DEG C with the heating rate of 5 DEG C/min, keeps 4h, cooling
It is taken out to room temperature.
There is resulting materials carbon nanometer layer to be cross-linked with each other into three dimensional skeletal structure, and silicon nano is distributed in carbon nanometer layer
In.Carbon nanometer layer is porous carbon nanosheet layer, and the lamellar spacing of carbon nanometer layer is 50-100nm, porous carbon nanosheet layer
Length and width is respectively 20nm-5 μm, porosity 1.1-1.3cm3/ g, aperture size is in the range of 0.5nm-8nm；Silicon is received
The grain size of rice corpuscles is 50nm..Contain N element in carbon nanometer layer, the mass content of N element is 2%-5%, while also containing different
Prime element P accounts for total mass content as 2%-5%.
Embodiment 4
The nano-silicon of surface modification and the preparation of amino-compound dispersion liquid：Under conditions of ice-water bath, to 40mL dioxygens
The 10mL concentrated sulfuric acids are added in water, are stirred evenly, then add in 0.8g simple substance silicon nanoparticle (30nm), continue to stir 8h, centrifugation
Washing obtains processed silicon nanoparticle after dry；The processed silicon nanoparticles of 0.5g is taken to be added to 100mL absolute ethyl alcohols
In, 3mLKH550 is slowly added dropwise in ultrasonic disperse 30min, 90 DEG C of stirrings of water-bath, and constant temperature stirring 12h is cooled down, filtered, made after dry
The silicon nanoparticle of KH550 surface modifications is obtained, weighs the silicon nanoparticle 250mg of surface modification in round-bottomed flask, is added in
120mL ethyl alcohol and 8.19g melamines, are sufficiently stirred 1.5h,
The preparation of carbon-silicon composite material：6.8g pentaerythrites are weighed in flask, add in 29.40g phosphoric acid, vacuum distillation
(vacuum degree 0.1MPa), stirring are heated to 150 DEG C, keep the temperature 1.5h, obtain the thick pentaerythritol phosphate of pale yellow transparent
Liquid.The nano-silicon of the surface modification obtained in upper step and amino-compound dispersion liquid are poured into equipped with wherein, are heated to 80 DEG C,
10h is stirred at reflux, obtains white emulsion, the big white solid of rotary evaporation.
Carbon nanometer layer coats the preparation of silicon materials：By white solid, quartz boat is put in, under nitrogen atmosphere, 5 DEG C/min's
Heating rate is warming up to 400 DEG C, keeps 0.5h, continues to be warming up to 1050 DEG C with the heating rate of 5 DEG C/min, keeps 8h, cooling
It is taken out to room temperature.
There is resulting materials carbon nanometer layer to be cross-linked with each other into three dimensional skeletal structure, and silicon nano is distributed in carbon nanometer layer
In.Carbon nanometer layer is porous carbon nanosheet layer, and the lamellar spacing of carbon nanometer layer is 50-60nm, porous carbon nanosheet layer
Length and width is respectively 20nm-5 μm, porosity 0.5-2cm3/ g, aperture size is in the range of 0.5nm-8nm；Silicon nanometer
The grain size of particle is 30nm..Contain N element in carbon nanometer layer, the mass content of N element is 2%-5%, while also containing heterogeneous
Element P accounts for total mass content as 2%-5%.
Claims (10)
1. a kind of lithium ion battery negative material, it is characterised in that：Material of the material for carbon nanometer layer coated Si, the material
There is material carbon nanometer layer to be cross-linked with each other into three dimensional skeletal structure, and silicon nano is distributed in carbon nanometer layer.
2. lithium ion battery negative material as described in claim 1, it is characterised in that：The carbon nanometer layer is porous carbon nanometer
Lamella, the lamellar spacing of the carbon nanometer layer is 10-300nm, and the length and width and width of porous carbon nanosheet layer are respectively 20nm-
5 μm, porosity 0.5-2cm3/ g, aperture size is in the range of 0.5nm-20nm；The grain size of silicon nano is 10-100nm.
3. lithium ion battery negative material as described in claim 1, it is characterised in that：Contain N element in the carbon nanometer layer, together
When one or more of also containing heterogeneous element P, S, B；The mass content of N element is 1%- in the carbon nanometer layer
10%, total mass content of one or more of described heterogeneous element P, S, B are 1%-10%.
4. a kind of preparation method of any lithium ion battery negative materials of claim 1-3, it is characterised in that：Including following
Step,
(1) preparation of the nano-silicon of surface modification and amino-compound dispersion liquid：Disperse in absolute ethyl alcohol surface treated
Nano-silicon powder, heating water bath while, add in coupling agent in dispersion liquid, and constant temperature stirring 8-16h postcooling filtration dryings obtain table
The nano-silicon of face modification, gained nano-silicon and amino-compound are disperseed in a solvent；
(2) preparation of carbon-silicon composite material：Polyalcohol and inorganic acid are uniformly mixed and brought it about after heated under vacuum
Esterification is added in esterification reaction product added with the amino-compound of the nano-silicon of surface modification obtained by step (1)
Dispersion liquid, again heating bring it about salt-forming reaction, obtain carbon-silicon composite material；
(3) preparation of carbon nanometer layer cladding silicon materials：Carbon-silicon composite material obtained by step (2) is carbonized in inert atmosphere high temperature
Processing obtains carbon nanometer layer cladding silicon materials.
5. the preparation method of lithium ion battery negative material as claimed in claim 4, it is characterised in that：Step is received described in (1)
Rice Si powder surface treatment method is under conditions of -4 DEG C to 4 DEG C of water-bath, and the concentrated sulfuric acid is added in into hydrogen peroxide, is uniformly mixed
Simple substance nano-silicon powder is added in afterwards, again the nano-silicon powder after washed, dry surface treatment after mixing.
6. the preparation method of lithium ion battery negative material as claimed in claim 4, it is characterised in that：It is double described in step (1)
The mass fraction of oxygen water is 25%-35%, and the mass fraction of the concentrated sulfuric acid is 90-98%；The volume ratio of the concentrated sulfuric acid and hydrogen peroxide is
5:1-10:1, the addition of simple substance silicon nanoparticle is the 5-20mg/mL concentrated sulfuric acids.
7. lithium ion battery negative material as claimed in claim 4 and preparation method thereof, it is characterised in that：Step (1) described idol
Connection agent is one or more of Silane coupling agent KH550, silane coupling agent 902, silane coupling agent 910；Nano silica fume
Mass concentration of the end in absolute ethyl alcohol dispersion liquid is 0.2-3mg/mL；The coupling agent and the volume ratio of absolute ethyl alcohol added in be
1：20-1：80；The temperature of heating water bath is 50-80 DEG C.
8. the preparation method of lithium ion battery negative material as claimed in claim 4, it is characterised in that：Step (1) described amino
Compound is urea, one or more kinds of in melamine, cyanamide, amino acid；In the dispersion liquid of the amino-compound
The mixed liquor that solvent is water, one or more kinds of in methanol, ethyl alcohol, ethylene glycol；The amino-compound is in surface modification
Mass concentration in the dispersion liquid of nano-silicon is 2-6g/mL；Mass concentration of the nano-silicon of surface modification in dispersion liquid is 1-
10mg/mL；
Polyalcohol described in step (2) is pentaerythrite, one or more kinds of in xylitol, sorbierite；The inorganic acid is
Mass concentration 20-90% boric acid, mass concentration 20-85% phosphoric acid, mass concentration 20-98% sulfuric acid, mass concentration 20-80% nitre
It is one or more kinds of in acid；The ratio of the amount of the substance of polyalcohol and inorganic acid is 2 in the step (1)：1-1：8；The ammonia
Based compound and the ratio of the amount of the substance of inorganic acid before esterification are 5：1-1：5.
9. the preparation method of lithium ion battery negative material as claimed in claim 4, it is characterised in that：Ester described in step (2)
Change the condition of reaction to react 0.5-5h, vacuum degree 0.03-0.2Mpa at 70-200 DEG C；The salt-forming reaction condition is
2-24h is reacted at a temperature of 30-150 DEG C；Carbonization treatment condition described in step (3) is keeps 0.5- under the conditions of 300-600 DEG C
3h increases temperature to 700-1100 DEG C from room temperature, and heating rate is 2-10 DEG C/min, keeps this temperature 0.5-3h, is cooled to room
Temperature；Inert atmosphere described in step (3) is nitrogen, argon gas or nitrogen and the gaseous mixture of argon gas.
10. a kind of application of any lithium ion battery negative materials of claim 1-3, it is characterised in that：The material should
In lithium ion battery.
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| CN114883551A (en) * | 2022-07-11 | 2022-08-09 | 深圳索理德新材料科技有限公司 | Alumina-coated nano silicon and continuous preparation method and system thereof |
| CN116885144A (en) * | 2023-08-21 | 2023-10-13 | 深圳市明盛新能源科技有限公司 | Silicon-carbon composite material for lithium battery cathode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114883551A (en) * | 2022-07-11 | 2022-08-09 | 深圳索理德新材料科技有限公司 | Alumina-coated nano silicon and continuous preparation method and system thereof |
| CN114883551B (en) * | 2022-07-11 | 2022-09-27 | 深圳索理德新材料科技有限公司 | Alumina-coated nano silicon and continuous preparation method and system thereof |
| CN116885144A (en) * | 2023-08-21 | 2023-10-13 | 深圳市明盛新能源科技有限公司 | Silicon-carbon composite material for lithium battery cathode material and preparation method thereof |
| CN116885144B (en) * | 2023-08-21 | 2024-04-16 | 深圳市明盛新能源科技有限公司 | Silicon-carbon composite material for lithium battery cathode material and preparation method thereof |
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| Publication number | Publication date |
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| CN108183198B (en) | 2020-04-10 |
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