CN105226241A - 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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- CN105226241A CN105226241A CN201410425859.7A CN201410425859A CN105226241A CN 105226241 A CN105226241 A CN 105226241A CN 201410425859 A CN201410425859 A CN 201410425859A CN 105226241 A CN105226241 A CN 105226241A
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Abstract
The invention discloses a kind of silicon-carbon composite cathode material of lithium ion battery, comprise nano-silicon, nano-sized carbon and base material, described nano-silicon accounts for 0.1% ~ 90% of described negative material gross mass; One deck nano-sized carbon is superposed as a hierarchical element on one deck nano-silicon, 2 ~ 10 described hierarchical element superpositions form multilayer coating structure and are coated on described substrate surface, such negative material has good electrical contact performance, and has excellent cycle performance.The invention also discloses a kind of preparation method of silicon-carbon composite cathode material of lithium ion battery, the method comprises the coated of coated, the nano-sized carbon of nano-silicon and repeats the step such as coated of nano-silicon and nano-sized carbon, negative material of good performance can be obtained, this preparation method is simple and easy to control, is easy to suitability for industrialized production.
Description
Technical field
The present invention relates to lithium ion battery negative material, particularly a kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof.
Background technology
Along with society and scientific and technological development, lithium ion battery negative material is also regenerated in continuous renewal.Originally, commercial lithium-ion batteries mainly adopts graphite-like material with carbon element as negative electrode active material.But, carbon class negative material is because of its specific capacity lower (372mAh/g), electronics miniaturization can not be met and the requirement such as vehicle lithium ion battery is high-power, high power capacity, thus need the Novel cathode material for lithium ion battery with high-energy-density, high safety performance, long circulation life researching and developing alternative material with carbon element.
So people are using conventional metals silicon as lithium ion battery negative material, and its theoretical specific capacity can reach 4200mAh/g, achieves high power capacity.But it exists volumetric expansion (about 300%) in charge and discharge process, can cause active particle efflorescence, and then loses electrical contact and cause capacity rapid decay, the conductivity of silicon materials itself is also poor simultaneously.
For above problem, solution conventional is at present that silicon is carried out nanometer, and silicon and carbon are carried out compound, but the performance impact of the mode of nanometer and silicon-carbon compound to material is larger.As the application number Chinese patent that is 200510082822.X disclose a kind of there is spherical nucleocapsid carbon-silicon composite material and method for making and purposes, the precursor pulp of superfine silica powder with hard carbon or soft carbon mixes by it, evaporating solvent is dry, namely obtains product in sintering carbonization.The Si-C composite material that the method is obtained, the shortcoming of existing Si-C composite material cycle performance difference is had some improvement, but larger cushioning effect is not played in hard carbon or the volumetric expansion/contraction of soft carbon to silicon, and the contact of silicon and soft carbon or hard carbon is not closely, the cycle performance of Si-C composite material still can not be satisfied the demands.
And for example application number be 201210534860.4 Chinese patent disclose a kind of preparation method of graphene coated silicon-carbon composite cathode material, nano-silicon and graphite microparticles join in graphene oxide dispersion by it, suspension is carried out spraying dry pelletizing, obtains class spherical precursor; Presoma sinters under an inert atmosphere and obtains graphene coated Si-C composite material.Si-C composite material prepared by the method, nano-silicon is easily exposed to material surface, and the contact of nano-silicon and Graphene or graphite is not closely, therefore limited to the improvement of cycle performance.
Summary of the invention
The object of the present invention is to provide the lithium ion battery negative material that a kind of structure is simple, have excellent cycling performance, not good to solve the electrical contact performance caused because of silicon volumetric expansion in prior art, the technical problem of cycle performance difference, the present invention simultaneously also correspondingly proposes a kind of preparation method of lithium ion battery negative material simple to operation.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of silicon-carbon composite cathode material of lithium ion battery, comprise nano-silicon, nano-sized carbon and base material, described nano-silicon accounts for 0.1% ~ 90% of described negative material gross mass; On one deck nano-silicon, superpose one deck nano-sized carbon as a hierarchical element, 2 ~ 10 described hierarchical element superpositions form multilayer coating structure and are coated on described substrate surface;
Wherein, described base material is material with carbon element A and/or material with carbon element B, described material with carbon element A be selected from Graphene, carbon nano-tube and carbon fiber one or more, described material with carbon element B be selected from native graphite, Delanium, carbonaceous mesophase spherules, soft carbon and hard carbon one or more.
Above-mentioned negative material, at the coated one deck nano-silicon of above-mentioned substrate surface, coated one deck nano-sized carbon on nano-silicon, coated one deck nano-silicon and nano-sized carbon successively in above-mentioned nano-sized carbon again, ..., repeatedly, form multilayer coating structure, by designing such multilayer coating structure, using the buffer body of nano-sized carbon as nano-silicon volumetric expansion, achieve while raising silicone content, decrease silicon and to expand the Volumetric expansion brought, ensure that negative material of the present invention also has good electrical contact performance and cycle performance while having high power capacity.
And, correspondingly, a kind of preparation method of silicon-carbon composite cathode material of lithium ion battery, it comprises following preparation process:
Nano-silicon coated: select above-mentioned base material, by chemical vapour deposition technique, above-mentioned nano-silicon is deposited on described substrate surface, obtain product one;
Nano-sized carbon coated: by chemical vapour deposition technique, above-mentioned nano-sized carbon is deposited on described product one surface, obtains product two;
Multi-layer nano silicon and nano-sized carbon coated: to the encapsulation steps of described product two successively nano-silicon described in repetitive operation and the encapsulation steps of described nano-sized carbon, number of repetition is 1 ~ 9 time, makes described base material coated by above-mentioned multilayer coating structure, obtained thick product;
Classification is selected: carried out by described thick product pulverizing, sieve, classification, obtains described silicon-carbon composite cathode material of lithium ion battery.
Above-mentioned preparation method is simple and easy to control, with low cost, is suitable for industrialization and batch production.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is silicon-carbon composite cathode material of lithium ion battery structure 1 schematic diagram;
Fig. 2 is silicon-carbon composite cathode material of lithium ion battery structure 2 schematic diagram;
Fig. 3 is silicon-carbon composite cathode material of lithium ion battery structure 3 schematic diagram;
Fig. 4 is silicon-carbon composite cathode material of lithium ion battery structure 4 schematic diagram;
Fig. 5 is the SEM figure of the silicon-carbon composite cathode material of lithium ion battery that embodiment 1 obtains;
Fig. 6 is the SEM figure of the silicon-carbon composite cathode material of lithium ion battery that embodiment 2 obtains;
Fig. 7 is the SEM figure of the silicon-carbon composite cathode material of lithium ion battery that embodiment 3 obtains;
Wherein 1: material with carbon element A; 2: material with carbon element B; 3: nano-silicon; 4: nano-sized carbon.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The silicon-carbon composite cathode material of lithium ion battery that the embodiment of the present invention provides, comprises nano-silicon, nano-sized carbon and base material, it is characterized in that, described nano-silicon accounts for 0.1% ~ 90% of described negative material gross mass; On one deck nano-silicon, superpose one deck nano-sized carbon as a hierarchical element, 2 ~ 10 described hierarchical element superpositions form multilayer coating structure and are coated on described substrate surface;
Particularly, described base material is material with carbon element A and/or material with carbon element B, described material with carbon element A be selected from Graphene, carbon nano-tube and carbon fiber one or more, described material with carbon element B be selected from native graphite, Delanium, carbonaceous mesophase spherules, soft carbon and hard carbon one or more, material with carbon element B preferred size is 2-50um's.Therefore, we can select Graphene and carbon fiber as described base material, also carbon nano-tube, Delanium and soft carbon can be selected as described base material, soft carbon and hard carbon can also be selected as described base material, etc., and during selection Graphene, preferably select lamellar spacing to be 0.33-50nm, when selecting carbon nano-tube, preferably select diameter to be single wall or the multi-walled carbon nano-tubes of 1-500nm, when selecting carbon fiber, preferred diameter is the carbon fiber of 1-1000nm.
In described negative material, silicone content (i.e. mass percent) is 0.1%-90%, can be such as 50%, 60%, 70-85% etc., the negative material of described nucleocapsid structure can be made like this to have higher capacity.
Above-mentioned nano-silicon and nano-sized carbon are coated on described substrate surface successively layer by layer, form multilayer coating structure.Described nano-silicon can preferred particulates shape or film-form, and during graininess, preferred size is the nano-silicon of 1-500nm, and during film-form, preferred thickness is the nano-silicon of 0.5-500nm.Described nano-sized carbon can preferred film shape, is that the nano-sized carbon film of 0.5-500nm is best especially with thickness.
Enumerate 4 kinds of different negative material structures below, to set forth technical solution of the present invention better.
See Fig. 1, negative material is nucleocapsid structure, core is material with carbon element B, described material with carbon element B is spherical or class is spherical, and described material with carbon element B Surface coating has one deck silicon nanoparticle layer, described silicon nanoparticle layer superposes one deck nano-sized carbon film, described nano-sized carbon film one deck silicon nanoparticle layer and nano-sized carbon thin layer have been superposed again successively, form multilayer coating structure, as shown in Figure 1, described multilayer coating structure is containing three hierarchical elements.
See Fig. 2, negative material is nucleocapsid structure, core is material with carbon element B, described material with carbon element B is spherical or class is spherical, described nano-silicon is film-form, and described nano-sized carbon is also film-form, on described material with carbon element B surface successively coated formation multilayer coating structure, as seen from the figure, described multilayer coating structure is containing three hierarchical elements.
See Fig. 3, negative material is sheet, and described material with carbon element A in the form of sheets, described nano-silicon is graininess, and described nano-sized carbon is film-form, superposes coated formation multilayer coating structure successively on described material with carbon element A surface, as seen from the figure, described multilayer coating structure is containing three hierarchical elements.
See Fig. 4, negative material is sheet, and described material with carbon element A in the form of sheets, described nano-silicon is film-form, and described nano-sized carbon is also film-form, superposes coated formation multilayer coating structure successively on described material with carbon element A surface, as seen from the figure, described multilayer coating structure is containing three hierarchical elements.
Multilayer coating structure in above-mentioned negative material, nano-silicon can fully be contacted with nano-sized carbon, improve contact area and the contact performance of nano-silicon and nano-sized carbon, be conducive to cushioning to the full extent nano-silicon embedding/de-lithium time the Swelling and contraction that produces, when particularly in silicon-carbon composite cathode material, nano-silicon content is higher, compare existing silicon-carbon composite cathode material, do not affect material circulation performance because of the increase of silicone content, but, nano-silicon and nano-sized carbon laminated construction are more conducive to cushioning the Swelling and contraction that nano-silicon produces when embedding/de-lithium, make silicon-carbon composite cathode material under high power capacity, still have excellent 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, and it comprises following preparation process:
S01. nano-silicon is coated: select above-mentioned base material, by chemical vapour deposition technique, above-mentioned nano-silicon is deposited on described substrate surface, obtains product one;
S02. nano-sized carbon is coated: by chemical vapour deposition technique, above-mentioned nano-sized carbon is deposited on described product one surface, obtains product two;
S03. multi-layer nano silicon and nano-sized carbon is coated: to the encapsulation steps of described product two successively nano-silicon described in repetitive operation and the encapsulation steps of described nano-sized carbon, number of repetition is 1 ~ 9 time, make described base material coated by above-mentioned multilayer coating structure, obtained thick product;
S04. classification is selected: carried out by described thick product pulverizing, sieve, classification, obtains described silicon-carbon composite cathode material of lithium ion battery.
Particularly, in described step S01, as previously mentioned, described base material is material with carbon element A and/or material with carbon element B, described material with carbon element A be selected from Graphene, carbon nano-tube and carbon fiber one or more, described material with carbon element B be selected from native graphite, Delanium, carbonaceous mesophase spherules, soft carbon and hard carbon one or more.We can completing steps S01 by the following method: first choose base material, again the base material chosen is put into the environment (can be 0 ~-0.1MPa for normal pressure or vacuum degree) being connected with silicon source gas, hydrogen and inert gas, heat 0.5 ~ 10 hour in 400 ~ 800 DEG C, obtain described product one, wherein, the volume ratio of described silicon source gas, hydrogen and inert gas is 0.2 ~ 5:1:10 ~ 20, the preferred SiH of described silicon source gas
4, SiHCl
3, SiH
2cl
2in one or more.
In above-mentioned steps S02, the coated of described nano-sized carbon can realize by the following method: described product one is put into the environment being connected with carbon-source gas, hydrogen and inert gas, heat 0.5 ~ 10 hour in 500 ~ 1000 DEG C, obtain described product two, wherein, the volume ratio of described carbon-source gas, hydrogen and inert gas is 0.2 ~ 5:1:10 ~ 20, one or more in the preferred acetylene of described carbon-source gas, ethene, methane.
In above-mentioned steps S01 and S02, inert gas can select in common nitrogen, argon gas, helium one or more.
In above-mentioned steps S02, the product two of formation is containing one deck nano-silicon coating layer and one deck nano-carbon coated layer, and namely substrate surface is coated with a hierarchical element.In step S03, described product two is carried out above-mentioned steps S01 and S02 more successively, namely repeats once, obtain the thick product containing two hierarchical elements, if repetitive operation 2-9 time, correspondingly can obtain the thick product of 3-10 hierarchical element.
In above-mentioned steps S04, described thick product carried out pulverize, sieve, classification, select granularity to be the negative material of 2-60um, namely 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, achieve the multilayer coating structure of nano-sized carbon and nano-silicon, substantially enhance the contact performance of nano-silicon and nano-sized carbon, be conducive to the expansion of valid cache nano-silicon in embedding/lithium ionic insertion/deinsertion process and contraction, improve the cycle performance of material, particularly can ensure that material still has excellent cycle performance under high power capacity.
Now for concrete silicon-carbon composite cathode material of lithium ion battery, the present invention is further elaborated.
Embodiment 1
(1) 200g spherical natural graphite is put into be connected with SiH
4, H
2with in the atmospheric pressure environment of Ar, SiH
4flow be 10ml/min, H
2flow is 10ml/min, Ar flow was 200ml/min, 500 DEG C of heating 0.5 hour;
(2) product of step (1) is put into again pass into C
2h
2, H
2with in the atmospheric pressure environment of Ar, C
2h
2flow be 10ml/min, H
2flow is 10ml/min, Ar flow was 200ml/min, 750 DEG C of heating 1 hour;
(3) repeat to the product of step (2) operation carrying out step (1) and step (2) successively, number of repetition is 2 times;
(4) product of step (3) pulverized, sieve, classification obtains silicon-carbon composite cathode material of lithium ion battery.
As shown in Figure 5, the surface topography map of the material of embodiment 1, there is nano silicon particles on visible spherical graphite surface.
Known by the performance test results of the negative material of embodiment in table 11, the present embodiment negative material also has excellent cycle performance under higher capacity, specifically, the silicon-carbon composite cathode material of lithium ion battery of the laminated construction adopting embodiment 1 obtained, mix according to the weight ratio of 90:6:4 with binding agent LA132 glue, conductive agent Super-P, add appropriate deionized water as dispersant furnishing slurry, be coated on Copper Foil, and through vacuumize, roll-in, punching, be prepared into pole piece, adopt metal lithium sheet to electrode, electrolyte adopts 1mol/LLiPF
6three components mixed solvent EC:DMC:EMC=1:1:1 (volume ratio), barrier film adopts microporous polypropylene membrane, is assembled into CR2016 button cell, and cycle performance test uses the current density of 100mA/g to carry out constant current constant voltage electric discharge and constant current charge.
Embodiment 2
(1) 20g carbon fiber is put into be connected with SiH
3cl, H
2with in the atmospheric pressure environment of Ar, SiH
3the flow of Cl is 10ml/min, H2 flow be 25ml/min, Ar flow was 200ml/min, 460 DEG C of heating 0.5 hour;
(2) product of step (1) is put into again pass into C
2h
2, H
2with in the atmospheric pressure environment of Ar, C
2h
2flow be 10ml/min, H
2flow is 15ml/min, Ar flow was 200ml/min, 700 DEG C of heating 1 hour;
(3) repeat to the product of step (2) operation carrying out step (1) and step (2) successively, number of repetition is 3 times;
(4) product of step (3) pulverized, sieve, classification obtains silicon-carbon composite cathode material of lithium ion battery.
As shown in Figure 6, the surface topography map of the material of embodiment 2, visible carbon fiber has nano silicon particles.
Known by the performance test results of the negative material of the embodiment 2 in table 1, the present embodiment negative material also has excellent cycle performance under higher capacity, specifically, the silicon-carbon composite cathode material of lithium ion battery of the laminated construction adopting embodiment 2 obtained, with binding agent LA132 glue, conductive agent Super-P mixes according to the weight ratio of 80:15:5, add appropriate deionized water as dispersant furnishing slurry, be coated on Copper Foil, and through vacuumize, roll-in, punching, be prepared into pole piece, metal lithium sheet is adopted to electrode, electrolyte adopts 1mol/LLiPF
6three components mixed solvent EC:DMC:EMC=1:1:1 (volume ratio), barrier film adopts microporous polypropylene membrane, is assembled into CR2016 button cell, and cycle performance test uses the current density of 100mA/g to carry out constant current constant voltage electric discharge and constant current charge.
Embodiment 3
(1) 10g Graphene is put into be connected with SiH
2cl
2, H
2with in the atmospheric pressure environment of Ar, SiH
2cl
2flow be 5ml/min, H
2flow is 20ml/min, Ar flow was 200ml/min, 450 DEG C of heating 1 hour;
(2) product of step (1) is put into again pass into C
2h
2, H
2with in the atmospheric pressure environment of Ar, C
2h
2flow be 5ml/min, H
2flow is 20ml/min, Ar flow was 200ml/min, 750 DEG C of heating 1 hour;
(3) repeat to the product of step (2) operation carrying out step (1) and step (2) successively, number of repetition is 5 times;
(4) product of step (3) pulverized, sieve, classification obtains silicon-carbon composite cathode material of lithium ion battery.
As shown in Figure 7, the surface topography map of the material of embodiment 3, visible graphene sheet layer has nano silicon particles.
Known by the performance test results of the negative material of the embodiment 3 in table 1, the present embodiment negative material also has excellent cycle performance under higher capacity, specifically, adopt the silicon-carbon composite cathode material of lithium ion battery that embodiment 3 is obtained, mix according to the weight ratio of 80:15:5 with binding agent LA132 glue, conductive agent Super-P, add appropriate deionized water as dispersant furnishing slurry, be coated on Copper Foil, and through vacuumize, roll-in, punching, be prepared into pole piece, adopt metal lithium sheet to electrode, electrolyte adopts 1mol/LLiPF
6three components mixed solvent EC:DMC:EMC=1:1:1 (volume ratio), barrier film adopts microporous polypropylene membrane, is assembled into CR2016 button cell, and cycle performance test uses the current density of 100mA/g to carry out constant current constant voltage electric discharge and constant current charge.
Embodiment 4
(1) 100g carbonaceous mesophase spherules is put into be connected with SiH
4, H
2with in the vacuum environment of Ar, vacuum degree is-0.05MPa, SiH
4flow be 8ml/min, H
2flow is 10ml/min, Ar flow was 200ml/min, 520 DEG C of heating 1 hour;
(2) product of step (1) is put into again pass into C
2h
2, H
2with in the vacuum environment of Ar, vacuum degree is-0.05MPa, C
2h
2flow be 10ml/min, H
2flow is 10ml/min, Ar flow was 200ml/min, 750 DEG C of heating 1 hour;
(3) repeat to the product of step (2) operation carrying out step (1) and step (2) successively, number of repetition is 3 times;
(4) product of step (3) pulverized, sieve, classification obtains silicon-carbon composite cathode material of lithium ion battery.
Known by the performance test results of the negative material of the embodiment 4 in table 1, the present embodiment negative material also has excellent cycle performance under higher capacity, specifically, adopt the silicon-carbon composite cathode material of lithium ion battery that embodiment 4 is obtained, mix according to the weight ratio of 90:6:4 with binding agent LA132 glue, conductive agent Super-P, add appropriate deionized water as dispersant furnishing slurry, be coated on Copper Foil, and through vacuumize, roll-in, punching, be prepared into pole piece, adopt metal lithium sheet to electrode, electrolyte adopts 1mol/LLiPF
6three components mixed solvent EC:DMC:EMC=1:1:1 (volume ratio), barrier film adopts microporous polypropylene membrane, is assembled into CR2016 button cell, and cycle performance test uses the current density of 100mA/g to carry out constant current constant voltage electric discharge and constant current charge.
The performance test results is as follows:
The chemical property of the battery that each embodiment material of table 1 is made
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a silicon-carbon composite cathode material of lithium ion battery, comprises nano-silicon, nano-sized carbon and base material, it is characterized in that, described nano-silicon accounts for 0.1% ~ 90% of described negative material gross mass; On one deck nano-silicon, superpose one deck nano-sized carbon as a hierarchical element, 2 ~ 10 described hierarchical element superpositions form multilayer coating structure and are coated on described substrate surface;
Wherein, described base material is material with carbon element A and/or material with carbon element B, described material with carbon element A be selected from Graphene, carbon nano-tube and carbon fiber one or more, described material with carbon element B be selected from native graphite, Delanium, carbonaceous mesophase spherules, soft carbon and hard carbon one or more.
2. silicon-carbon composite cathode material of lithium ion battery as claimed in claim 1, it is characterized in that, described nano-silicon is graininess or film-form, and during graininess, granularity is 1-500nm, and during film-form, thickness is 0.5-500nm.
3. silicon-carbon composite cathode material of lithium ion battery as claimed in claim 1, it is characterized in that, described nano-sized carbon is film-form, and thickness is 0.5-500nm.
4. the silicon-carbon composite cathode material of lithium ion battery as described in any one of claim 1-3, is characterized in that, the lamellar spacing of described Graphene is 0.33-50nm.
5. the silicon-carbon composite cathode material of lithium ion battery as described in any one of claim 1-3, is characterized in that, described carbon nano-tube is single wall or many walls, and the diameter of described carbon nano-tube is 1-500nm.
6. a preparation method for silicon-carbon composite cathode material of lithium ion battery, is characterized in that, comprises following preparation process:
Nano-silicon coated: select base material described in claim 1, by chemical vapour deposition technique, nano-silicon described in any one of claim 1-3 is deposited on described substrate surface, obtains product one;
Nano-sized carbon coated: by chemical vapour deposition technique, nano-sized carbon described in any one of claim 1-3 is deposited on described product one surface, obtains product two;
Multi-layer nano silicon and nano-sized carbon coated: to the encapsulation steps of described product two successively nano-silicon described in repetitive operation and the encapsulation steps of described nano-sized carbon, number of repetition is 1 ~ 9 time, make described base material coated by multilayer coating structure described in claim 1, obtained thick product;
Classification is selected: carried out by described thick product pulverizing, sieve, classification, obtains described silicon-carbon composite cathode material of lithium ion battery.
7. the preparation method of silicon-carbon composite cathode material of lithium ion battery as claimed in claim 6, it is characterized in that, the encapsulation steps of described nano-silicon is specially, described base material is put into the environment being connected with silicon source gas, hydrogen and inert gas, heat 0.5 ~ 10 hour in 400 ~ 800 DEG C, obtain described product one, wherein, the volume ratio of described silicon source gas, hydrogen and inert gas is 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 characterized in that, the encapsulation steps of described nano-sized carbon is specially, described product one is put into the environment being connected with carbon-source gas, hydrogen and inert gas, heat 0.5 ~ 10 hour in 500 ~ 1000 DEG C, obtain described product two, wherein, the volume ratio of described carbon-source gas, hydrogen and inert gas 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 characterized in that, described silicon source gas is selected from SiH
4, SiHCl
3, SiH
2cl
2in one or more.
10. the preparation method of silicon-carbon composite cathode material of lithium ion battery as claimed in claim 8, is characterized in that, described carbon-source gas be selected from acetylene, ethene, methane one or more.
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| CN107069009A (en) * | 2017-04-24 | 2017-08-18 | 广东烛光新能源科技有限公司 | A kind of silicon-carbon cathode material and preparation method thereof |
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| CN109244377A (en) * | 2017-07-10 | 2019-01-18 | 力信（江苏）能源科技有限责任公司 | A kind of preparation method of negative electrode of lithium ion battery Si-C composite material |
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| 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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| CN107093719B (en) * | 2017-04-24 | 2019-11-05 | 广东烛光新能源科技有限公司 | A kind of silicon-carbon cathode material and preparation method thereof |
| CN107093719A (en) * | 2017-04-24 | 2017-08-25 | 广东烛光新能源科技有限公司 | A kind of silicon-carbon cathode material and preparation method thereof |
| 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 |
| CN107069009A (en) * | 2017-04-24 | 2017-08-18 | 广东烛光新能源科技有限公司 | A kind of silicon-carbon cathode material and preparation method thereof |
| CN109244378A (en) * | 2017-07-10 | 2019-01-18 | 力信（江苏）能源科技有限责任公司 | A kind of preparation method of porous nano Si-C composite material |
| CN109244377A (en) * | 2017-07-10 | 2019-01-18 | 力信（江苏）能源科技有限责任公司 | A kind of preparation method of negative electrode of lithium ion battery Si-C 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 |
| CN109360962A (en) * | 2018-10-24 | 2019-02-19 | 郑州中科新兴产业技术研究院 | A kind of lithium battery high stability silicon-carbon cathode material and preparation method thereof |
| CN111164804A (en) * | 2019-12-30 | 2020-05-15 | 上海杉杉科技有限公司 | Silicon-based negative electrode material, preparation method thereof and lithium ion battery |
| WO2021134197A1 (en) * | 2019-12-30 | 2021-07-08 | 上海杉杉科技有限公司 | Silicon-based negative electrode material and preparation method therefor, and lithium ion battery |
| 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 |
| CN111244410A (en) * | 2020-01-16 | 2020-06-05 | 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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