CN105226241B - A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof - Google Patents
A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of silicon-carbon composite cathode material of lithium ion battery, including nano-silicon, nano-sized carbon and base material, the nano-silicon accounts for the 0.1%~90% of the negative material gross mass；One layer of nano-sized carbon is superimposed on using one layer of nano-silicon as a hierarchical element, 2~10 hierarchical elements are superimposed and to form multilayer coating structure and be coated on the substrate surface, and such negative material has good electrical contact performance, and with excellent cycle performance.The invention also discloses a kind of preparation method of silicon-carbon composite cathode material of lithium ion battery, the method step such as including the cladding of the cladding of nano-silicon, the cladding of nano-sized carbon and repetition nano-silicon and nano-sized carbon, negative material of good performance can be obtained, the preparation method is simple and easy to control, it is easy to industrialized production.
Description
Technical field
The present invention relates to lithium ion battery negative material, more particularly to a kind of silicon-carbon composite cathode material of lithium ion battery and
Its preparation method.
Background technology
With the development of society and science and technology, lithium ion battery negative material is also constantly updating the replacement.Originally, commercialization lithium
Ion battery is mainly using graphite-like carbon material as negative electrode active material.However, carbons negative material is relatively low because of its specific capacity
(372mAh/g), it is impossible to meet the requirement such as electronics miniaturization and the high-power, high power capacity of automobile-used lithium ion battery, so that
Research and develop alternative carbon material with high-energy-density, high safety performance, long circulation life new type lithium ion battery negative pole material
Material.
Then, people using conventional metals silicon as lithium ion battery negative material, its theoretical specific capacity is up to 4200mAh/
G, realizes high power capacity.But there is volumetric expansion (about 300%) in it, can cause active particle efflorescence in charge and discharge process, enter
And lose electrical contact and cause capacity rapid decay, while silicon materials electric conductivity in itself is also poor.
For problem above, conventional solution is that silicon is carried out into nanosizing at present, and silicon is combined with carbon,
But nanosizing and the compound mode of silicon-carbon are larger to the performance impact of material.China such as Application No. 200510082822.X is special
Profit discloses a kind of carbon-silicon composite material with spherical nucleocapsid and its preparation method and purposes, its by superfine silica powder and hard carbon or
The precursor pulp mixing of soft carbon, evaporation solvent is dried, and product is obtained final product in sintering carbonization.Silicon-carbon composite wood obtained in the method
Material, the shortcoming to existing Si-C composite material cycle performance difference has some improvement, but hard carbon or soft carbon to the volumetric expansion of silicon/
Larger cushioning effect is not played in contraction, and silicon contact with soft carbon or hard carbon is not closely so that silicon-carbon composite wood
The cycle performance of material still can not meet demand.
And for example the Chinese patent of Application No. 201210534860.4 discloses a kind of graphene coated silicon-carbon composite cathode
The preparation method of material, be added in graphene oxide dispersion for nano-silicon and graphite microparticles, suspension sprayed by it
Pelletizing is dried, spherical presoma is obtained；Presoma sinters obtain graphene coated Si-C composite material under an inert atmosphere.Should
Si-C composite material prepared by method, nano-silicon is easily exposed to material surface, and nano-silicon contact with Graphene or graphite
Not closely, it is therefore limited to the improvement of cycle performance.
The content of the invention
It is an object of the invention to provide a kind of simple structure, the lithium ion battery negative material with excellent cycling performance
Material, with solve in the prior art because caused by silicon volumetric expansion electrical contact performance it is not good, cycle performance difference technical problem, while
The present invention also correspondingly proposes a kind of preparation method of lithium ion battery negative material simple to operation.
In order to realize foregoing invention purpose, technical scheme is as follows：
A kind of silicon-carbon composite cathode material of lithium ion battery, including nano-silicon, nano-sized carbon and base material, the nano-silicon account for institute
State the 0.1%~90% of negative material gross mass；One layer of nano-sized carbon an as hierarchical element, 2 is superimposed on using one layer of nano-silicon
~10 hierarchical elements are superimposed and to form multilayer coating structure and be coated on the substrate surface；
Wherein, the base material is carbon material A and/or carbon material B, the carbon material A are selected from Graphene, CNT and carbon
One or more in fiber, the carbon material B is selected from native graphite, Delanium, carbonaceous mesophase spherules, soft carbon and hard
One or more in carbon.
Above-mentioned negative material, one layer of nano-silicon is coated in above-mentioned substrate surface, and one layer of nano-sized carbon is coated on nano-silicon, then
Coat one layer of nano-silicon and nano-sized carbon successively in above-mentioned nano-sized carbon ..., repeatedly, multilayer coating structure is formed, lead to
The such multilayer coating structure of design is crossed, using nano-sized carbon as the buffer body of nano-silicon volumetric expansion, is realized and is contained in raising silicon
While amount, the Volumetric expansion that silicon expansion brings is reduced, it is ensured that negative material of the present invention is with the same of high power capacity
When also have good electrical contact performance and cycle performance.
And, correspondingly, a kind of preparation method of silicon-carbon composite cathode material of lithium ion battery, it includes that following preparation walks
Suddenly：
The cladding of nano-silicon：Above-mentioned base material is selected, above-mentioned nano-silicon is deposited on by the base by chemical vapour deposition technique
Material surface, obtains product one；
The cladding of nano-sized carbon：Above-mentioned nano-sized carbon is deposited on by the surface of the product one by chemical vapour deposition technique, is obtained
Product two；
The cladding of multi-layer nano silicon and nano-sized carbon：It is repeated in operating the encapsulation steps of the nano-silicon to the product two
With the encapsulation steps of the nano-sized carbon, number of repetition is 1~9 time so that the base material is coated by above-mentioned multilayer coating structure, system
Obtain crude product；
Classification selection：The crude product is crushed, sieved, be classified, obtained the lithium ion battery silicon-carbon Compound Negative
Pole material.
Above-mentioned preparation method is simple and easy to control, with low cost, is suitable to industrialize and produces in batches.
Brief description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing：
Fig. 1 is the schematic diagram of silicon-carbon composite cathode material of lithium ion battery structure 1；
Fig. 2 is the schematic diagram of silicon-carbon composite cathode material of lithium ion battery structure 2；
Fig. 3 is the schematic diagram of silicon-carbon composite cathode material of lithium ion battery structure 3；
Fig. 4 is the schematic diagram of silicon-carbon composite cathode material of lithium ion battery structure 4；
Fig. 5 schemes for the SEM of silicon-carbon composite cathode material of lithium ion battery obtained in embodiment 1；
Fig. 6 schemes for the SEM of silicon-carbon composite cathode material of lithium ion battery obtained in embodiment 2；
Fig. 7 schemes for the SEM of silicon-carbon composite cathode material of lithium ion battery obtained in embodiment 3；
Wherein 1：Carbon material A；2：Carbon material B；3：Nano-silicon；4：Nano-sized carbon.
Specific embodiment
In order that the technical problem to be solved in the present invention, technical scheme and beneficial effect become more apparent, below in conjunction with
Embodiment and accompanying drawing, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used
To explain the present invention, it is not intended to limit the present invention.
Silicon-carbon composite cathode material of lithium ion battery provided in an embodiment of the present invention, including nano-silicon, nano-sized carbon and base material,
Characterized in that, the nano-silicon accounts for the 0.1%~90% of the negative material gross mass；To be superimposed one layer on one layer of nano-silicon
Used as a hierarchical element, 2~10 hierarchical elements are superimposed and to form multilayer coating structure and be coated on the base material nano-sized carbon
Surface；
Specifically, the base material is carbon material A and/or carbon material B, the carbon material A be selected from Graphene, CNT and
One or more in carbon fiber, the carbon material B be selected from native graphite, Delanium, carbonaceous mesophase spherules, soft carbon and
One or more in hard carbon, carbon material B preferred sizes are 2-50um's.Therefore, we can select Graphene and carbon
Fiber is used as the base material, it is also possible to CNT, Delanium and soft carbon are selected as the base material, it is also an option that soft carbon
With hard carbon as described base material, etc., and during selection Graphene, it is 0.33-50nm to be preferably selected lamellar spacing, selects carbon
During nanotube, the single wall or multi-walled carbon nano-tubes of a diameter of 1-500nm are preferably selected, during selection carbon fiber, preferably a diameter of 1-
The carbon fiber of 1000nm.
In the negative material, silicone content (i.e. mass percent) is 0.1%-90%, for example can be 50%,
60%th, 70-85% etc., can so cause the negative material of the core shell structure has capacity higher.
Above-mentioned nano-silicon and nano-sized carbon are coated on the substrate surface layer by layer successively, form multilayer coating structure.The nano-silicon
Can preferably graininess or film-form, preferred size is the nano-silicon of 1-500nm during graininess, and preferred thickness is during film-form
The nano-silicon of 0.5-500nm.The nano-sized carbon can be with preferred film shape, the nanometer C film especially with thickness as 0.5-500nm
Most preferably.
4 kinds of different negative material structures are set forth below, preferably to illustrate technical solution of the present invention.
Referring to Fig. 1, negative material is core shell structure, core be carbon material B, the carbon material B be it is spherical or spherical, it is described
Carbon material B surface is coated with one layer of silicon nanoparticle layer, and one layer of nanometer C film is superimposed on the silicon nanoparticle layer, described to receive
One layer of silicon nanoparticle layer and nanometer carbon thin film layer have been sequentially overlapped on rice C film again, multilayer coating structure has been formed, can by Fig. 1
Know, the multilayer coating structure contains three hierarchical elements.
Referring to Fig. 2, negative material is core shell structure, core be carbon material B, the carbon material B be it is spherical or spherical, it is described
Nano-silicon is film-form, and the nano-sized carbon is also film-form, coats to form multilayer coating structure knot successively in the carbon material B surface
Structure, as seen from the figure, the multilayer coating structure contains three hierarchical elements.
Referring to Fig. 3, negative material is sheet, and in the form of sheets, the nano-silicon is graininess, the nanometer to the carbon material A
Carbon is film-form, and being sequentially overlapped cladding on the carbon material A surfaces forms multilayer coating structure, as seen from the figure, the multilayer bag
Structure is covered containing three hierarchical elements.
Referring to Fig. 4, negative material is sheet, and in the form of sheets, the nano-silicon is film-form, the nanometer to the carbon material A
Carbon is also film-form, is sequentially overlapped cladding on the carbon material A surfaces and forms multilayer coating structure, as seen from the figure, the multilayer
Clad structure contains three hierarchical elements.
Multilayer coating structure in above-mentioned negative material so that nano-silicon can be contacted fully with nano-sized carbon, improve nanometer
The contact area and contact performance of silicon and nano-sized carbon, are conducive to buffering to the full extent that nano-silicon produces in Li insertion extraction is swollen
Swollen and contraction, when particularly nanometer silicone content is higher in silicon-carbon composite cathode material, compared to existing silicon-carbon composite cathode material, and
Material circulation performance is influenceed without the increase because of silicone content, but, nano-silicon and nano-sized carbon laminated construction are more beneficial for delaying
Rush expansion and contraction that nano-silicon is produced in Li insertion extraction so that silicon-carbon composite cathode material still has excellent under high power capacity
Different cycle performance.
Correspondingly, the embodiment of the present invention additionally provides a kind of preparation method of silicon-carbon composite cathode material of lithium ion battery,
It includes following preparation process：
S01. the cladding of nano-silicon：Above-mentioned base material is selected, above-mentioned nano-silicon is deposited on by institute by chemical vapour deposition technique
Substrate surface is stated, product one is obtained；
S02. the cladding of nano-sized carbon：Above-mentioned nano-sized carbon is deposited on by the surface of the product one by chemical vapour deposition technique,
Obtain product two；
S03. the cladding of multi-layer nano silicon and nano-sized carbon：It is repeated in operating the cladding of the nano-silicon to the product two
The encapsulation steps of step and the nano-sized carbon, number of repetition is 1~9 time so that the base material is by above-mentioned multilayer coating structure bag
Cover, crude product is obtained；
S04. classification selection：The crude product is crushed, sieved, be classified, obtained the lithium ion battery silicon-carbon and answer
Close negative material.
Specifically, in the step S01, as it was previously stated, the base material is carbon material A and/or carbon material B, the carbon
Materials A be selected from Graphene, CNT and carbon fiber in one or more, the carbon material B be selected from native graphite, people
Make one or more in graphite, carbonaceous mesophase spherules, soft carbon and hard carbon.We can by the following method complete step
S01：First choose base material, then the base material that will be chosen be put into being connected with the environment of silicon source gas, hydrogen and inert gas (can be with
For normal pressure or vacuum are 0~-0.1MPa), heated 0.5~10 hour in 400~800 DEG C, the product one is obtained, its
In, the volume ratio of the silicon source gas, hydrogen and inert gas is 0.2~5：1：10~20, the preferred SiH of silicon source gas4、
SiHCl3、SiH2Cl2In one or more.
In above-mentioned steps S02, the cladding of the nano-sized carbon can be realized by the following method：The product one is put into
It is connected with the environment of carbon-source gas, hydrogen and inert gas, is heated 0.5~10 hour in 500~1000 DEG C, obtains the product
Product two, wherein, the volume ratio of the carbon-source gas, hydrogen and inert gas is 0.2~5：1：10~20, the carbon-source gas are excellent
Select one or more in acetylene, ethene, methane.
In above-mentioned steps S01 and S02, inert gas can select the one kind or one kind in common nitrogen, argon gas, helium
More than.
In above-mentioned steps S02, the product two of formation contains one layer of nano-silicon clad and one layer of nano-carbon coated layer, i.e.,
Substrate surface is coated with a hierarchical element.In step S03, the product two is carried out successively again above-mentioned steps S01 and
S02, that is, be repeated once, and obtains containing two crude products of hierarchical element, if repeating 2-9 times, can accordingly obtain 3-10
The crude product of hierarchical element.
In above-mentioned steps S04, the crude product is crushed, sieved, be classified, selection granularity is the negative pole of 2-60um
Material, that is, obtain the silicon-carbon composite cathode material of lithium ion battery described in the embodiment of the present invention.
Above-mentioned preparation method is simple and easy to apply, realizes the multilayer coating structure of nano-sized carbon and nano-silicon, substantially enhances nano-silicon
With the contact performance of nano-sized carbon, be conducive to expansion and contraction of the valid cache nano-silicon during Li insertion extraction ion, improve
The cycle performance of material, particularly can guarantee that material still has excellent cycle performance under high power capacity.
Now by taking specific silicon-carbon composite cathode material of lithium ion battery as an example, the present invention will be described in further detail.
Embodiment 1
(1) 200g spherical natural graphites are put into and are connected with SiH4、H2In the atmospheric pressure environment of Ar, SiH4Flow be 10ml/
Min, H2Flow is 10ml/min, and Ar flows are 200ml/min, are heated 0.5 hour at 500 DEG C；
(2) product of step (1) is placed into and is passed through C2H2、H2In the atmospheric pressure environment of Ar, C2H2Flow be 10ml/
Min, H2Flow is 10ml/min, and Ar flows are 200ml/min, are heated 1 hour at 750 DEG C；
(3) product to step (2) repeats to carry out the operation of step (1) and step (2) successively, and number of repetition is 2 times；
(4) product to step (3) is crushed, sieved, is classified and obtain silicon-carbon composite cathode material of lithium ion battery.
As shown in figure 5, the surface topography map of the material of embodiment 1, it is seen that there are nano silicon particles on spherical graphite surface.
By the performance test results of the negative material of embodiment 1 in table 1, the present embodiment negative material is higher
Also there is excellent cycle performance, specifically, using the lithium ion battery silicon-carbon of laminated construction obtained in embodiment 1 under capacity
Composite negative pole material, with binding agent LA132 glue, conductive agent Super-P according to 90：6：4 weight adds appropriate going than mixing
Ionized water is tuned into slurry as dispersant, is coated on Copper Foil, and vacuum dried, roll-in, punching, pole piece is prepared into, to electricity
Pole uses metal lithium sheet, and electrolyte uses 1mol/LLiPF6Three component mixed solvent EC:DMC:EMC=1:1:1 (volume
Than), barrier film uses microporous polypropylene membrane, is assembled into CR2016 button cells, and cycle performance test is close using the electric current of 100mA/g
Degree carries out constant current constant voltage electric discharge and constant-current charge.
Embodiment 2
(1) 20g carbon fibers are put into and are connected with SiH3Cl、H2In the atmospheric pressure environment of Ar, SiH3The flow of Cl is 10ml/
Min, H2 flow are 25ml/min, and Ar flows are 200ml/min, are heated 0.5 hour at 460 DEG C；
(2) product of step (1) is placed into and is passed through C2H2、H2In the atmospheric pressure environment of Ar, C2H2Flow be 10ml/
Min, H2Flow is 15ml/min, and Ar flows are 200ml/min, are heated 1 hour at 700 DEG C；
(3) product to step (2) repeats to carry out the operation of step (1) and step (2) successively, and number of repetition is 3 times；
(4) product to step (3) is crushed, sieved, is classified and obtain silicon-carbon composite cathode material of lithium ion battery.
As shown in fig. 6, the surface topography map of the material of embodiment 2, it is seen that there is nano silicon particles on carbon fiber.
By the performance test results of the negative material of the embodiment 2 in table 1, the present embodiment negative material is higher
Capacity under also have excellent cycle performance, specifically, using the lithium ion battery silicon of laminated construction obtained in embodiment 2
Carbon compound cathode materials, with binding agent LA132 glue, conductive agent Super-P according to 80：15：5 weight is added appropriate than mixing
Deionized water be tuned into slurry as dispersant, be coated on Copper Foil, and vacuum dried, roll-in, punching, be prepared into pole piece,
Metal lithium sheet is used to electrode, electrolyte uses 1mol/LLiPF6Three component mixed solvent EC:DMC:EMC=1:1:1 (body
Product ratio), barrier film uses microporous polypropylene membrane, is assembled into CR2016 button cells, and cycle performance test uses the electric current of 100mA/g
Density carries out constant current constant voltage electric discharge and constant-current charge.
Embodiment 3
(1) 10g Graphenes are put into and are connected with SiH2Cl2、H2In the atmospheric pressure environment of Ar, SiH2Cl2Flow be 5ml/
Min, H2Flow is 20ml/min, and Ar flows are 200ml/min, are heated 1 hour at 450 DEG C；
(2) product of step (1) is placed into and is passed through C2H2、H2In the atmospheric pressure environment of Ar, C2H2Flow be 5ml/
Min, H2Flow is 20ml/min, and Ar flows are 200ml/min, are heated 1 hour at 750 DEG C；
(3) product to step (2) repeats to carry out the operation of step (1) and step (2) successively, and number of repetition is 5 times；
(4) product to step (3) is crushed, sieved, is classified and obtain silicon-carbon composite cathode material of lithium ion battery.
As shown in fig. 7, the surface topography map of the material of embodiment 3, it is seen that there is nano silicon particles on graphene sheet layer.
By the performance test results of the negative material of the embodiment 3 in table 1, the present embodiment negative material is higher
Capacity under also have excellent cycle performance, specifically, using lithium ion battery silicon-carbon composite negative pole obtained in embodiment 3
Material, with binding agent LA132 glue, conductive agent Super-P according to 80：15：5 weight adds appropriate deionized water than mixing
Slurry is tuned into as dispersant, is coated on Copper Foil, and vacuum dried, roll-in, punching, pole piece is prepared into, electrode is used
Metal lithium sheet, electrolyte uses 1mol/LLiPF6Three component mixed solvent EC:DMC:EMC=1:1:1 (volume ratio), barrier film
Using microporous polypropylene membrane, CR2016 button cells are assembled into, cycle performance test carries out perseverance using the current density of 100mA/g
Stream constant voltage discharge and constant-current charge.
Embodiment 4
(1) 100g carbonaceous mesophase spherules are put into and are connected with SiH4、H2In the vacuum environment of Ar, vacuum is -0.05MPa,
SiH4Flow be 8ml/min, H2Flow is 10ml/min, and Ar flows are 200ml/min, are heated 1 hour at 520 DEG C；
(2) product of step (1) is placed into and is passed through C2H2、H2In the vacuum environment of Ar, vacuum is -0.05MPa,
C2H2Flow be 10ml/min, H2Flow is 10ml/min, and Ar flows are 200ml/min, are heated 1 hour at 750 DEG C；
(3) product to step (2) repeats to carry out the operation of step (1) and step (2) successively, and number of repetition is 3 times；
(4) product to step (3) is crushed, sieved, is classified and obtain silicon-carbon composite cathode material of lithium ion battery.
By the performance test results of the negative material of the embodiment 4 in table 1, the present embodiment negative material is higher
Capacity under also have excellent cycle performance, specifically, using lithium ion battery silicon-carbon composite negative pole obtained in embodiment 4
Material, with binding agent LA132 glue, conductive agent Super-P according to 90：6：4 weight adds appropriate deionized water to make than mixing
For dispersant is tuned into slurry, it is coated on Copper Foil, and vacuum dried, roll-in, punching, pole piece is prepared into, to electrode using gold
Category lithium piece, electrolyte uses 1mol/LLiPF6Three component mixed solvent EC:DMC:EMC=1:1:1 (volume ratio), barrier film is adopted
With microporous polypropylene membrane, CR2016 button cells are assembled into, cycle performance test carries out constant current using the current density of 100mA/g
Constant voltage discharge and constant-current charge.
The performance test results are as follows：
The chemical property of the battery that each embodiment material of table 1 is made
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of silicon-carbon composite cathode material of lithium ion battery, including nano-silicon, nano-sized carbon and base material, it is characterised in that described
Nano-silicon accounts for the 0.1%~90% of the negative material gross mass；One layer of nano-sized carbon is superimposed on using one layer of nano-silicon as one
Hierarchical element, 2~10 hierarchical elements are superimposed and to form multilayer coating structure and be coated on the substrate surface；
Wherein, the base material is carbon material A and/or carbon material B, the carbon material A are selected from Graphene, CNT and carbon fiber
In one or more, the carbon material B be selected from native graphite, Delanium, carbonaceous mesophase spherules, soft carbon and hard carbon in
One or more.
2. silicon-carbon composite cathode material of lithium ion battery as claimed in claim 1, it is characterised in that the nano-silicon is particle
Shape or film-form, granularity is 1-500nm during graininess, and thickness is 0.5-500nm during film-form.
3. silicon-carbon composite cathode material of lithium ion battery as claimed in claim 1, it is characterised in that the nano-sized carbon is film
Shape, thickness is 0.5-500nm.
4. the silicon-carbon composite cathode material of lithium ion battery as described in claim any one of 1-3, it is characterised in that the graphite
The lamellar spacing of alkene is 0.33-50nm.
5. the silicon-carbon composite cathode material of lithium ion battery as described in claim any one of 1-3, it is characterised in that the carbon is received
Mitron is single wall or many walls, a diameter of 1-500nm of the CNT.
6. a kind of preparation method of silicon-carbon composite cathode material of lithium ion battery, it is characterised in that including following preparation process：
The cladding of nano-silicon：Base material described in selection claim 1, by chemical vapour deposition technique by claim any one of 1-3
The nano-silicon is deposited on the substrate surface, obtains product one；
The cladding of nano-sized carbon：Nano-sized carbon described in claim any one of 1-3 is deposited on by the product by chemical vapour deposition technique
The surface of product one, obtains product two；
The cladding of multi-layer nano silicon and nano-sized carbon：It is repeated in operating encapsulation steps and the institute of the nano-silicon to the product two
The encapsulation steps of nano-sized carbon are stated, number of repetition is 1~9 time so that the base material is by multilayer coating structure bag described in claim 1
Cover, crude product is obtained；
Classification selection：The crude product is crushed, sieved, be classified, obtained the lithium ion battery silicon-carbon composite negative pole material
Material.
7. the preparation method of silicon-carbon composite cathode material of lithium ion battery as claimed in claim 6, it is characterised in that described to receive
The encapsulation steps of rice silicon are connected with the environment of silicon source gas, hydrogen and inert gas specifically, the base material is put into, 400
Heated 0.5~10 hour in~800 DEG C, obtain the product one, wherein, the body of the silicon source gas, hydrogen and inert gas
Product is than being 0.2~5：1：10~20.
8. the preparation method of silicon-carbon composite cathode material of lithium ion battery as claimed in claims 6 or 7, it is characterised in that institute
State the encapsulation steps of nano-sized carbon and be connected with the environment of carbon-source gas, hydrogen and inert gas specifically, the product one is put into,
Heated 0.5~10 hour in 500~1000 DEG C, obtain the product two, wherein, the carbon-source gas, hydrogen and indifferent gas
The volume ratio of body is 0.2~5：1：10~20.
9. the preparation method of silicon-carbon composite cathode material of lithium ion battery as claimed in claim 7, it is characterised in that the silicon
Source gas is selected from SiH4、SiHCl3、SiH2Cl2In one or more.
10. the preparation method of silicon-carbon composite cathode material of lithium ion battery as claimed in claim 8, it is characterised in that described
Carbon-source gas be selected from acetylene, ethene, methane in one or more.
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| CN107069009B (en) * | 2017-04-24 | 2020-02-11 | 广东烛光新能源科技有限公司 | Silicon-carbon negative electrode material and preparation method thereof |
| CN109244377A (en) * | 2017-07-10 | 2019-01-18 | 力信（江苏）能源科技有限责任公司 | Preparation method of lithium ion battery cathode silicon-carbon composite material |
| CN109244378A (en) * | 2017-07-10 | 2019-01-18 | 力信（江苏）能源科技有限责任公司 | Preparation method of porous nano silicon-carbon composite material |
| WO2019016395A1 (en) | 2017-07-21 | 2019-01-24 | Imerys Graphite & Carbon Switzerland Ltd. | Carbon-coated silicon oxide / graphite composite particles, as well as preparation methods and applications of the same |
| CN109360962B (en) * | 2018-10-24 | 2021-02-12 | 郑州中科新兴产业技术研究院 | High-stability silicon-carbon negative electrode material for lithium battery and preparation method thereof |
| CN111164804B (en) * | 2019-12-30 | 2021-11-26 | 上海杉杉科技有限公司 | Silicon-based negative electrode material, preparation method thereof and lithium ion battery |
| CN111244410B (en) * | 2020-01-16 | 2022-05-27 | 兰溪致德新能源材料有限公司 | Lithium battery negative electrode material and preparation method thereof |
| CN114678507A (en) * | 2022-04-12 | 2022-06-28 | 南昌大学共青城光氢储技术研究院 | Multi-layer silicon/carbon film negative electrode plate of lithium ion battery and preparation method thereof |
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