CN107026258A - SiO/C combination electrode materials of conductive support load and its preparation method and application - Google Patents
SiO/C combination electrode materials of conductive support load and its preparation method and application Download PDFInfo
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- CN107026258A CN107026258A CN201610066076.3A CN201610066076A CN107026258A CN 107026258 A CN107026258 A CN 107026258A CN 201610066076 A CN201610066076 A CN 201610066076A CN 107026258 A CN107026258 A CN 107026258A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to SiO/C combination electrode materials of conductive support load and its preparation method and application, the combination electrode material includes：Conductive support, the silicon oxide layer being carried in the conductive support and the conductive coating for being coated on the silicon oxide layer surface.The composite based on silica of the present invention is as a result of conductive support as template, and the composite of gained is advantageously implemented its big multiplying power work for constituting battery by with excellent electron conduction；Moreover, the SiO/ conductive coating structures of conductive support support are more beneficial for bulk strain of the buffers active material in cyclic process, more excellent cyclical stability is realized.
Description
Technical field
The invention belongs to nano material preparation/electrode material preparation/energy storage device field, class conductive support support relate to
SiOx@C negative materials, preparation method and the chargeable lithium cell being made up of the negative material.
Background technology
Lithium ion battery realizes commercialization so far first by Sony Corporation since 1991, as energy supply part in electronic product
With huge success is achieved on the small-sized electric vehicles.In recent years, with electronics industry fast development and Large Electric is handed over
The appearance of logical instrument, requirements at the higher level are proposed to the energy density of lithium ion battery, power density, security and life-span etc..Just
For energy density, it depends primarily on the reversible capacity of used in battery electrode material and the voltage difference of positive and negative interpolar.At present, may be used
Selective positive electrode system is relatively limited, and their available capacity is generally relatively low, the smaller (higher capacity of room for promotion
Positive electrode will be based on new battery system, such as lithium sulphur (Li-S) battery or metal-air battery)；It is different from positive electrode
It is that the available negative material of lithium battery also has very big selection space, and they also have very big carry in terms of reversible capacity
Between lift-off.Such as silica-base material, with the nearly theoretical capacity for decupling commercial Carbon anode capacity (372mAh/g) at present (up to 3579
MAh/g, room temperature), get more and more people's extensive concerning recently.On the basis of existing battery processing technology, if it is possible to silicon
Negative pole replaces Carbon anode, will can be greatly decreased the consumption of negative material in the battery, reduces negative pole shared body in the battery
Product, and can just increase the consumption of positive electrode in identical battery space (volume), so as to lift the energy density of battery.
In addition, selection silica-base material can also greatly improve the security of battery, because silica-base material is even in oxygen as negative pole
Under will not also burn.
But the practical application of Si base negative poles also faces many problems, most important of which is that can be produced when it is with lithium alloyage
Raw enormousness expansion (~400%) causes itself efflorescence so that lost on electrode between particle and particle or between particle and collector
Electrical contact, seriously damages the cyclical stability and reversible capacity of electrode (battery).For this problem, researcher is by substantial amounts of
Research finds, build such as particle, line pipe or nucleocapsid silicon nanostructure can effectively alleviate Si bulk strain, acquisition compared with
Excellent cyclical stability, but build Si based nano-materials and also face that cost is high, be difficult to the predicament that mass produces.In addition,
The problem of Si negative pole own electronic electric conductivity is poor is also one of important problem of solution needed for future trend actual use.
Except outside the pale of civilization by Si nanometers, there is researcher to propose use silica (being particularly SiO) as negative material, be on the one hand because
There is the theoretical capacity of~5 times of business graphite capacity for silica, be on the other hand because oxygen element contained therein exists
Oxide can be transformed into discharge process, the cushion of Si bulk strains is served as, and then improve the cyclical stability of Si electrodes.
Also the advantage of these two aspects is based on, SiO materials is turned into one of important system of exploitation high power capacity negative pole recently.
At present, the preparation method of high-purity SiO powder is highly developed, and conventional method is by silica and Si powder
SiO materials (chemistry world, 11,1993,533) are obtained by distillation, condensation at high temperature after mixing.What this method was obtained
SiO materials generally all have larger particle size, up to millimeter magnitude.Want to be used as electrode material, in addition it is also necessary to SiO
Post-processed, to improve its electric conductivity and cyclical stability.Common practice is will to be obtained in above-mentioned distillation-condensation process
SiO first carry out particle refinement, prepare micron-sized SiO particles, finally to micron particles surface carry out carbon coating processing make
For SiO electrode materials are gone out, as described in patent CN 103872303A.But it is this that-carbon coating work is crushed by the condensation-grinding that distils
The method and step that skill prepares SiO electrode materials is cumbersome, and SiO electrode material cyclical stabilities are not good enough.
The content of the invention
The problem that preparation and aspect of performance for high-performance SiO electrode materials are present, it is an object of the invention to provide one
Plant composite based on silica and preparation method thereof, the device for preparing the composite and include the composite
Negative electrode of lithium ion battery and lithium ion battery.
In a first aspect, the present invention provides a kind of composite based on silica, including：Conductive support, it is carried on institute
State the silicon oxide layer in conductive support and be coated on the conductive coating on the silicon oxide layer surface.
The present invention the composite (SiO composites) based on silica as a result of conductive support as template,
The composite of gained is advantageously implemented its big multiplying power work for constituting battery by with excellent electron conduction；Moreover, leading
The SiO/ conductive coating structures of electric support body supports are more beneficial for bulk strain of the buffers active material in cyclic process, realize
More excellent cyclical stability.
It is preferred that times in nano particle of the conductive support selected from elemental metals and carbon, line and pipe and graphene
Meaning is a kind of.
It is preferred that the thickness of the silicon oxide layer is 10nm~10 μm.
It is preferred that the silica has and SiO or Si and SiO on crystal structurexThe consistent feature of compound
Structure, wherein 0<x<2.
It is preferred that the conductive coating is carbon-coating and/or electroconductive polymer layer, preferably carbon coating layer.It is described conductive high
Molecule is preferably at least one of polyaniline, polypyrrole and Polyglycolic acid fibre based compound.
It is preferred that the thickness of the conductive coating is 1~200nm, preferably 5~50nm.
Second aspect, the present invention provides the preparation method of any one above-mentioned composite, comprises the following steps：
(1) heating provides the raw material of SiO gases and produces SiO steam to distil；
(2) condense the SiO steam of generation and be grown in formation conductive support-SiO materials in conductive support；And
(3) conductive coating is grown in obtained conductive support-SiO material surfaces by chemical gaseous phase depositing process, forms described
Composite；
Wherein step (1) is carried out with step (2) in two different reaction cavities.
Compared with existing SiO electrodes and preparation method thereof (distillation condensation-grinding crushes-carbon coating), advantages of the present invention exists
In：(1) this method can accurately control depositions of the SiO in supporter template, effectively prevent SiO particles too long
Greatly；(2) compared to traditional preparation process, particle size it is controllable, will be without particle thinning process, on the one hand can be by conductive layer
Cladding process is directly integrated into follow-up preparation flow to realize, is on the other hand also beneficial to improve the production effect of electrode material
Rate.
The third aspect, the present invention provides the device for preparing any one above-mentioned composite, including：
SiO distillation chambers for producing SiO steam；
With the SiO distil chamber be connected, for the SiO steam of generation is condensed be grown in conductive support formation conductive support-
The SiO condensation chambers of SiO materials；And
Be connected with the SiO condensation chambers, the conductive material bag for the conductive support-SiO material coated with conductive clads to generation
Cover chamber.
Fourth aspect, the present invention provides a kind of negative electrode of lithium ion battery, and it is by negative comprising any one above-mentioned composite
It is prepared by pole material.
The negative electrode of lithium ion battery of the present invention has higher reversible capacity and excellent cycling stability.
5th aspect, the present invention provides a kind of lithium ion battery, and it includes above-mentioned negative electrode of lithium ion battery.
Brief description of the drawings
The preparation facilities diagrammatic cross-section for the SiO/C electrode materials that Fig. 1 supports for the conductive support of the present invention, wherein
1 high temperature oxidation resisting aluminium sheet, 2 reactants, 3 waste gates, 4 reactant charging hoppers, the outer valve of 5 charging hoppers, 6 charging hoppers
Bleeding point, 7 charging hopper internal valves, 8 heating modules, 9 high temperature SiO steam leads, 10 regulating valves, 11 carbon template charging hoppers
Outer valve, 12 carbon template charging hoppers, 13 bleeding points, 14 charging hopper internal valves, 15 heating modules, 16SiO steam dispersing sieves
After step valve before net, 17 carbon template agitators, 18 condensation chamber metallic cavities, 19 transitional storehouses, 20 transitional storehouses, 21 transitional storehouses
Valve, 22 carbon coating chamber metallic cavities, 23 heated die plates, 24 steam vents, 25 discharging openings, 26 carbon-source gas air inlets,
27SiO composite agitators, 28 carbon-source gas disperse screen cloth；
The SiO/C material structure schematic diagrams that Fig. 2 supports for present invention gained conductive support；
Fig. 3 is the X-ray diffractogram of the CNT/SiO/C materials using CNT CNT as supporter obtained；
The charging and discharging curve that Fig. 4 is as negative pole for the CNT/SiO/C materials of acquisition；
Fig. 5 is the capacity maintenance characteristics of 40 circulations before structure SiO negative poles.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following embodiments, it should be appreciated that accompanying drawing and following embodiments are only
For illustrating the present invention, it is not intended to limit the present invention.
The present invention provides a kind of composite based on silica.The composite is using conductive support as template, by activity
Material SiO is deposited on template surface, and in active layer Surface coating a thin layer conductive coating.The composite has three layers
Feature structure：Internal layer is that conductive supporter, intermediate layer are that active material layer, outer layer are conductive coating.
Can be any type of, structure conductive material as conductive support, the conductive support material include but
It is not limited to nano particle, line and pipe and graphene of elemental metals and carbon etc..
As the silica of active material, it has and SiO or Si and SiO on crystal structure characteristicxCompound phase
Consistent feature, wherein 0<x<2.
The thickness of active material layer can for tens nanometer to a few micrometers, such as 10nm~10 μm.Active material layer can be by
Active material particle is constituted.
Can be any type of conductive materials as conductive coating, the conductive coating include but is not limited to carbon-coating,
Electroconductive polymer layer such as polyaniline, polypyrrole and Polyglycolic acid fibre based compound etc..Preferably, the conductive coating is carbon
Layer, i.e., described composite is the SiO/C composites that conductive support is supported.
The thickness of conductive coating can be several nanometers to 200 nanometers, preferably such as 1~200nm, 5~50nm.
The preparation method of the composite of the present invention can include SiO distillations, be combined (SiO with conductive support material pattern
Condensation) and conductive layer cladding (such as original position carbon coating) process.Specifically, using conductive support material as template, profit
It is directly loaded in the SiO characteristics easily distilled on conductive support material pattern, forms the load of tens nanometer to a few micrometers
Layer, finally in the conductive coating (such as carbon coating layer) of one layer several nanometers to tens nanometers of the active layer Surface coating, is formed
Composite (such as SiO/C composites of conductive support support).
Compared with prior art, method of the invention is most distinct feature is that SiO sublimation process and condensation process are separated
Carried out in two different reaction chambers, and two processes are in the differential responses position of same reaction chamber in existing method
(high and low warm area) is carried out.The active material particle size that is obtained of method of the present invention is controllable, good conductivity, structure are steady
It is fixed.
Raw material for producing SiO can be silicon oxide powder or the mixture of SiO 2 powder and silicon metal powder.To this
Raw material heats to produce SiO steam.
The SiO steam of generation is directed into another chamber containing conductive support, is condensed and shape in conductive support
Into SiO layer, conductive support-SiO materials are consequently formed.
The method of coated with conductive layer includes but is not limited to chemical vapour deposition technique on conductive support-SiO materials.With carbon bag
Exemplified by coating, in chemical vapour deposition technique, carbon source and argon gas are imported into chamber.Carbon source includes but is not limited to methane, second
Alkene, acetylene, propane, ethanol, acetone, benzene, toluene and their mixing.
In a specific example, the template that conductive support grows as SiO easily forms the spy of gas phase using SiO
Point, the steam that the SiO steams obtained in sublimation process are formed by sublimation process directly condensation, which is grown in conductive support, to be formed
Conductive support-SiO materials.Finally, then by CVD method in obtained conductive support-SiO material surfaces several receive is grown
Rice forms the SiO/C electrode materials of conductive support support to tens nanometers of carbon coating layer.In whole preparation process, lead to
After constantly changing conductive support, substantial amounts of conductive support-SiO materials can be prepared.By controlling conductive support to exist
Residence time in condensation chamber can regulate and control the amount of SiO in conductive support-SiO materials.
The most basic preparation equipment for being used for the composite of the present invention is characterized in different anti-of obvious three functions
Cavity is answered, respectively distils, condense and CVD cladding chambers.
Fig. 1 shows the preparation facilities diagrammatic cross-section of the SiO/C electrode materials of the conductive support support of the present invention.Such as Fig. 1
Shown in middle device profile, required equipment is main by three part structures such as SiO distillations chamber, SiO condensation chambers and CVD carbon coating chambers
Into.High temperature oxidation resisting aluminum pipe/plate constitutes the burner hearth 1 of SiO distillation chambers.Reactant SiO2Burner hearth is positioned over Si mixture 2
In 1, when temperature and pressure meets SiO sublimation conditions, the SiO steam of generation is equipped with the high temperature of heating module 8 via outer wall
Conduit 9 leads to SiO condensation chambers.During continuous production, constantly it can be reacted by reactant loading chamber 4 to the distillation addition of chamber 1
Thing 2.During filler, outer valve 5 is first opened, reactant is added into loading chamber 4, outer valve 5 is closed, extraction valve 6 is opened, will feed
Chamber 4 is evacuated in -0.1MPa, counter balance pocket with after the pressure of distillation intracavitary, opening internal valve 7, reactant being added into distillation
In chamber 1.The waste material produced in continuous production completes to clear up via discharging opening 3.
The SiO steam of above-mentioned generation via gas disperse screen cloth 16 enter condensation chamber, with constantly agitator 17 agitation under
Carbon template be compounded to form conductive support-SiO materials.Adjusting control valve 10 can control SiO steam to be in contact with carbon template
Time, realize SiO in carbon template load capacity regulation and control.Refractory metal plate 18 is constituted and filled on the inwall of condensation chamber, outer wall
Having heaters 15 and multi-layer heat preserving layer.During continuous production, continuous charging can be realized via charging hopper 12：Conductive support is passed through
Outer valve 11 enters after charging hopper 12, closes outer valve 11, and -0.1MPa be pumped to by bleeding point 13, balance bunker it is interior with it is cold
After the pressure of solidifying intracavitary, internal valve 14 is opened, conductive support is sent into condensation chamber.Finally, a certain amount of SiO conduction is loaded
Supporter delivers to transitional storehouse 20 by agitator 17, completes the recombination process of SiO and carbon.
Conductive support-SiO the materials formed in said process through transitional storehouse 20 enter CVD carbon coating chambers, 500 DEG C-
Under the conditions of 1000 DEG C, several nanometers to tens nanometers are formed in the cracking carbonization of conductive support-SiO material surfaces by carbon-source gas
Carbon coating layer, forms the SiO@C-materials of conductive support support.High temperature resistant quartz or metallic plate 22 constitute CVD carbon coatings
Carbon-source gas are mounted with chamber burner hearth, burner hearth and disperse screen cloth 28, its outside cladding having heaters 23 and heat-insulation layer.Agitator 27
Continuous agitation be conducive to forming uniform carbon coating layer on conductive support-SiO surfaces.The conductive supporting of carbon-coating is finally coated
The SiO/C materials of body support are collected via discharging opening 25, complete the preparation of whole material, the structure such as schematic diagram of resulting materials
Shown in 2.
The composite cyclical stability of the present invention is excellent, by taking the composite obtained by being supporter by CNT as an example,
Capacity is more than 800mAh/g after 40 circulations.The method of the invention preparation technology is simple, low raw-material cost, resulting materials
It can be used as the lithium ion battery negative material of high capacity type.
The silica composite material of the present invention can be used as lithium ion cell high-capacity negative pole.
The present invention also provide the negative material comprising the composite, the negative pole that is prepared by the negative material and comprising
The lithium battery of the negative pole.
Compared with existing SiO electrodes and preparation method thereof (distillation condensation-grinding crushes-carbon coating), advantages of the present invention exists
In：(1) this method can accurately control depositions of the SiO in supporter template, effectively prevent SiO particles too long
Greatly；(2) compared to traditional preparation process, particle size it is controllable, will be without particle thinning process, on the one hand can be by CVD
Carbon coating process is directly integrated into follow-up preparation flow to realize, is on the other hand also beneficial to improve the production of electrode material
Efficiency；(3) according to the SiO composites obtained by the inventive method as a result of conductive support as template, gained is answered
Condensation material is advantageously implemented its big multiplying power work for constituting battery by with excellent electron conduction；(4) conductive support branch
The SiO@C-structure of support are more beneficial for bulk strain of the buffers active material in cyclic process, realize more excellent stable circulation
Property.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this hair
It is bright to be further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to the present invention's
Some nonessential modifications and adaptations that the above is made belong to protection scope of the present invention.Following specific technique ginsengs of example
Number etc. is also only an example in OK range, i.e. those skilled in the art can be done in suitable scope by this paper explanation
Selection, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
The invention resulting materials and its characteristic are illustrated by taking CNT (CNT) as an example.By raw material SiO2You compare 1 with Si massages:1
Block is pressed into after mixing, distillation intracavitary is placed in, chamber is evacuated to~10Pa after, be heated to 1350 DEG C.The SiO now produced steams
Vapour flows to SiO condensation chambers through high temperature conduit and is combined with CNT, and agitation CNT makes one layer of SiO of its coated with uniform,
Resulting materials are designated as [email protected] compound tense, the vacuum of control distillation chamber makes it have identical vacuum with condensation chamber
Degree.Previously obtained CNT@SiO materials are sent into CVD carbon coating intracavitary.Under normal pressure, ethene is passed through by carbon source air inlet 26
(ratio is 1 with Ar gaseous mixture:300) after, cavity temperature is increased to 900 DEG C, and be incubated 1h.During this, ethene
The carbon coating layer to form about 40nm is cracked on CNT@SiO surfaces, resulting materials are designated as CNT@[email protected]. 3 is the material
The X-ray diffractogram of material, the CNT@SiO@C-materials for showing gained are the Si and the SiO of amorphous by crystallizingxTwo-phase structure
Into.
CNT@SiO@C-materials and conductive additive Super P and binding agent PVDF examples 8 in mass ratio will be obtained：1：
1 ground and mixed is uniform, forms cathode size.The slurry is coated on negative current collector copper foil, prepared after being dried through 100 DEG C
Go out available negative plate.Using lithium metal as to electrode, 1M LiPF6：EC-DMC (volume ratios 1:1) assembled for electrolyte
CR2025 button cells.Fig. 4 is the charging curve of corresponding button cell.Before Fig. 5 is the CNT@SiO@C negative poles of the structure
The capacity maintenance characteristics of 40 circulations.It can be seen that the oxidation silicon composite cathode prepared by this method has higher reversible capacity
With excellent cycling stability.
Claims (10)
1. a kind of composite based on silica, it is characterised in that including：Conductive support, the silicon oxide layer being carried in the conductive support and the conductive coating for being coated on the silicon oxide layer surface.
2. composite according to claim 1, it is characterised in that any one in nano particle of the conductive support selected from elemental metals and carbon, line and pipe and graphene.
3. composite according to claim 1 or 2, it is characterised in that the thickness of the silicon oxide layer is 10 nm~10 μm.
4. composite according to any one of claim 1 to 3, it is characterised in that the silica has and SiO or Si and SiO on crystal structurexThe consistent feature structure of compound, wherein 0<x<2.
5. composite according to any one of claim 1 to 4, it is characterised in that the conductive coating is carbon-coating and/or electroconductive polymer layer, preferably carbon coating layer；The conducting polymer is preferably at least one of polyaniline, polypyrrole and Polyglycolic acid fibre based compound.
6. composite according to any one of claim 1 to 5, it is characterised in that the thickness of the conductive coating is 1~200 nm, preferably 5~50 nm.
7. the preparation method of the composite any one of a kind of claim 1 to 6, it is characterised in that comprise the following steps：
（1）Heating provides the raw material of SiO gases and produces SiO steam to distil；
（2）Condense the SiO steam of generation and be grown in formation conductive support-SiO materials in conductive support；And
（3）Conductive coating is grown in obtained conductive support-SiO material surfaces by chemical gaseous phase depositing process, the composite is formed；
Wherein step（1）And step（2）Carried out in two different reaction cavities.
8. a kind of device for being used to prepare the composite any one of claim 1 to 6, it is characterised in that including：
SiO distillation chambers for producing SiO steam；
It is connected with SiO distillation chambers, for making the SiO steam condensation of generation be grown in the SiO condensation chambers of formation conductive support-SiO materials in conductive support；And
Be connected with the SiO condensation chambers, for the conductive support-SiO material coated with conductive clads to generation conductive material coat chamber.
9. a kind of negative electrode of lithium ion battery, is prepared as the negative material of the composite any one of comprising claim 1 to 6.
10. a kind of lithium ion battery, includes the negative electrode of lithium ion battery described in claim 9.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108365186A (en) * | 2018-01-11 | 2018-08-03 | 湖南立方新能源科技有限责任公司 | A kind of silicon substrate composite negative pole material and preparation method thereof |
| CN108539147A (en) * | 2018-03-21 | 2018-09-14 | 同济大学 | A kind of preparation method and application of lithium ion battery negative material SiO@Al@C |
| CN110240166A (en) * | 2019-07-04 | 2019-09-17 | 北华航天工业学院 | A kind of SiO2@C nano composite material and preparation method |
| CN111403740A (en) * | 2020-03-24 | 2020-07-10 | 洛阳联创锂能科技有限公司 | Preparation method of silica ink composite material |
| CN111689501A (en) * | 2020-06-23 | 2020-09-22 | 兰溪致德新能源材料有限公司 | Porous/hollow structure silicon-based anode material and preparation method thereof |
| CN112086630A (en) * | 2020-09-17 | 2020-12-15 | 浙江锂宸新材料科技有限公司 | Preparation method of silicon monoxide composite negative electrode material and product thereof |
| CN112320804A (en) * | 2020-09-29 | 2021-02-05 | 上海皓越电炉技术有限公司 | Vacuum heat treatment equipment for continuously preparing SiO negative electrode material of lithium ion battery |
| CN115810741A (en) * | 2021-12-28 | 2023-03-17 | 宁德时代新能源科技股份有限公司 | Negative active material, method of preparing the same, and secondary battery and device using the same |
| US11843110B2 (en) * | 2019-10-30 | 2023-12-12 | GM Global Technology Operations LLC | Methods for controlling formation of multilayer carbon coatings on silicon-containing electroactive materials for lithium-ion batteries |
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| CN108539147B (en) * | 2018-03-21 | 2021-01-12 | 同济大学 | Preparation method and application of lithium ion battery negative electrode material SiO @ Al @ C |
| CN110240166A (en) * | 2019-07-04 | 2019-09-17 | 北华航天工业学院 | A kind of SiO2@C nano composite material and preparation method |
| US11843110B2 (en) * | 2019-10-30 | 2023-12-12 | GM Global Technology Operations LLC | Methods for controlling formation of multilayer carbon coatings on silicon-containing electroactive materials for lithium-ion batteries |
| CN111403740A (en) * | 2020-03-24 | 2020-07-10 | 洛阳联创锂能科技有限公司 | Preparation method of silica ink composite material |
| CN111689501A (en) * | 2020-06-23 | 2020-09-22 | 兰溪致德新能源材料有限公司 | Porous/hollow structure silicon-based anode material and preparation method thereof |
| CN111689501B (en) * | 2020-06-23 | 2022-03-29 | 兰溪致德新能源材料有限公司 | Porous/hollow structure silicon-based anode material and preparation method thereof |
| CN112086630A (en) * | 2020-09-17 | 2020-12-15 | 浙江锂宸新材料科技有限公司 | Preparation method of silicon monoxide composite negative electrode material and product thereof |
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| CN115810741A (en) * | 2021-12-28 | 2023-03-17 | 宁德时代新能源科技股份有限公司 | Negative active material, method of preparing the same, and secondary battery and device using the same |
| WO2023124913A1 (en) * | 2021-12-28 | 2023-07-06 | 宁德时代新能源科技股份有限公司 | Negative electrode active material, preparation method therefor, and secondary battery and apparatus related thereto |
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