CN108807862A - A kind of silicon based composite material and preparation method thereof, negative material and lithium battery - Google Patents
A kind of silicon based composite material and preparation method thereof, negative material and lithium battery Download PDFInfo
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- CN108807862A CN108807862A CN201710307595.9A CN201710307595A CN108807862A CN 108807862 A CN108807862 A CN 108807862A CN 201710307595 A CN201710307595 A CN 201710307595A CN 108807862 A CN108807862 A CN 108807862A
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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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- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
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- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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 a kind of silicon based composite materials and preparation method thereof, and the preparation method comprises the following steps：(1) silica-base material is deposited in the surface homogenous gas-phase of carbon material；(2) carbon coating is carried out to step (1) resulting materials；(3) physics is carried out to step (2) resulting materials and removes magnetic treatment.The invention further relates to lithium ion battery negative materials and lithium battery comprising the silicon based composite material.The preparation method of the silicon based composite material of the present invention solves the problems, such as the preparation of silica-base material and evenly dispersed two; and have many advantages, such as that flow is simple, be easy to large-scale production, gained composite material shows excellent cycle performance and good high rate performance for lithium ion battery negative material.
Description
Technical field
The present invention relates to field of material technology more particularly to a kind of high magnification silicon based composite material and preparation method thereof, bear
Pole material and lithium battery.
Background technology
Lithium ion battery has gradually occupied portable consumer class since last century, the nineties was commercialized by Sony Corporation
Electronic market, in electric vehicle, energy storage field also has vast potential for future development.
With the development of technology, people propose increasingly the volume energy density and mass energy density of lithium ion battery
High requirement.However, lithium ion battery, since emerging, carbon material is always just the first choice of negative material, and graphite material
Theoretical capacity is only 372mAh/g, and the high-end product capacity of large-scale negative material producer each at present has been sufficiently close to theory appearance
Amount, therefore, exploitation novel anode material have become the trend of the times of current industry.
In many candidate materials, silicon materials are by its height ratio capacity, low cost, suitable removal lithium embedded current potential, abundant money
Source is widely considered next-generation ion cathode material lithium, however, its during removal lithium embedded close to 300% bulk strain
Its cycle performance is seriously affected, to solve the problems, such as this, people develop two technology paths, and one is absorb silicon with carbon material to answer
The compound route of silicon-carbon of change, another kind are the oxidation Asia silicon route in silica matrices by the silicon microcrystalline dispersion of 1-10nm.Value
It is noted that many studies demonstrate that, silicon materials particle is smaller, is more conducive to mitigate its ess-strain, however, nano material
It also brings preparations simultaneously, disperses and problem that specific surface area is excessive.
Invention content
Therefore, the purpose of the present invention is to the present situation for negative material, a kind of silicon based composite material and its preparation side are provided
Method, one step of the preparation method solve the problems, such as the preparation of nano material and evenly dispersed two, and simple with flow, are easy to
The characteristics of large-scale production, gained silicon based composite material for lithium ion battery negative material show excellent cycle performance and
Good high rate performance.
The purpose of the present invention is achieved through the following technical solutions.
On the one hand, the present invention provides a kind of preparation method of silicon based composite material, includes the following steps：
(1) silica-base material is deposited in the surface homogenous gas-phase of carbon material；
(2) carbon coating is carried out to step (1) resulting materials；
(3) physics is carried out to step (2) resulting materials and removes magnetic treatment.
Preferably, the silica-base material is by silicon and silica, and/or the sub- silicon of oxidation, and it is optional selected from B, Al,
The complex element of one or more of the elements such as Na, Mg, Ca, Ba, Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ge, Sn or
Its oxide of person is formed；It is highly preferred that the step (1) is under vacuum, silicon and silica, and/or oxidation is sub-
Silicon, and it is optional in the elements such as B, Al, Na, Mg, Ca, Ba, Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ge, Sn
One or more of complex elements or its oxide is heated to 1000-2000 degrees Celsius after mixing, preferably 1000~
It 1600 degrees Celsius, is deposited on the carbon material that temperature is 200-700 degrees Celsius.
Preferably, the carbon-coated mode of step (2) progress is selected from：
1) it in vapor deposition processes, is passed through one or more in gaseous carbon sources, is carbonized under 700-1100 degrees Celsius；
Or
2) after vapor deposition, by obtained material, either solid carbon source is mixed by solid phase or even in liquid phase with liquid
After conjunction, it is heat-treated under 700-1100 degrees Celsius.
Preferably, in the silicon based composite material, the mass fraction of carbon material is 10%-90%, the matter of silica-base material
Amount score is 1-80%, and the mass fraction of carbon coating layer is 5%-30%；It is highly preferred that in the silica-base material element silicon matter
Amount score is 40%-80%, and the mass fraction of oxygen element is 10%-60%；The mass fraction of complex element is 0%-40%.
Preferably, the carbon material is selected from soft carbon, hard carbon, carbonaceous mesophase spherules, graphitized intermediate-phase carbosphere, natural stone
The combination of one or more of ink, modified natural graphite, artificial graphite and porous graphite；It is highly preferred that the carbon material
Average grain diameter is 1-40 microns.
Preferably, the microstructure of the silica-base material is the silicon crystallite or silicon-base alloy crystallite Dispersed precipitate of 1-50nm
Among metal oxide and/or composite oxides parent phase.
Preferably, the silica-base material is formed by the mixture of silicon and silica, wherein mole of silicon and silica
Than being 1:2~2:1.
Preferably, the step (1) is deposited the oxidation Asia silicon of 20-2000nm or modified oxidized Asia on the carbon material
The particle of silicon or the material of film；It is highly preferred that the carbon material is graphite.
Preferably, the mode 1 of the step (2)) in, the gaseous carbon sources being passed through are in the gases such as toluene, methane, acetylene
It is one or more.Preferably, the mode 2 of the step (2)) in, the liquid or solid carbon source are sugar, pitch or polymer
Precursor；It is highly preferred that the sugar is glucose, the pitch is asphalt or mesophase pitch, body before the polymer
Body is phenolic resin or polyacrylonitrile.
In the present invention, term " complex element " refer to selected from B, Al, Na, Mg, Ca, Ba, Ti, Mn, Fe, Co, Ni, Cu,
One or more of the elements such as Zn, Zr, Mo, Ge, Sn, the element of silicon based composite material is formed together with silicon, oxygen element.
Term " polymer " precursor " refers to the polymer that can be carbonized to 700 degree or more in an inert atmosphere.
Term " mesophase pitch " refers to the substance of the pitch class with interphase.
Preferably, wherein the specific surface area for the material that the step (2) obtains is 2-20m2/ g, average grain diameter are 2-40 μ
M, shape are spherical shape, elliposoidal, cobble shaped and/or random polygon；And/or the silicon based composite material as lithium from
When sub- cell negative electrode material, charge specific capacity 400-1500mAh/g.
On the other hand, the present invention provides a kind of silicon based composite material prepared by the method by the present invention, and specific surface area is
2-20m2/ g, average grain diameter are 2-40 μm, and shape is spherical shape, elliposoidal, cobble shaped and/or random polygon.
Another aspect, the present invention provide a kind of lithium ion battery negative material, the silicon prepared by method of the present invention
Based composites or silicon based composite material of the present invention and carbon material composition.
Preferably, mass percent of the silicon based composite material in the lithium ion battery negative material is more than 2%；
It is highly preferred that the carbon material includes soft carbon, hard carbon, carbonaceous mesophase spherules, graphitized intermediate-phase carbosphere, natural graphite, changes
The combination of one or more of property natural graphite and artificial graphite.
In another aspect, the present invention provides a kind of lithium battery, include the silicon substrate composite wood prepared by method of the present invention
Material or silicon based composite material of the present invention or lithium ion battery negative material of the present invention.
Present invention uniform deposition silicon based composite material on the carbon material mitigates silicon based composite material using carbon material and is recycling
Ess-strain in the process, meanwhile, deposition process is also beneficial to increase interface binding power between the two, and prior
Be, vapor deposition processes of the invention compared with the prior art in first crushing after solid phase or liquid phase mixing can ensure silicon substrate
Composite material it is evenly dispersed, so as to the various characteristics preferably brought using the size of its Nano grade.According to this hair
The silicon based composite material of bright preparation combines the advantages of compound silicon-carbon and oxidation Asia silicon route, one side silica-base material inside 1-
The structure of the crystallite Dispersed precipitate of 50nm can greatly inhibit the expansion of silicon, and carbon material can integrally provide for silica-base material
Another buffering, and the carbon coating layer of material surface also can effectively inhibit the side reaction between silica-base material and electrolyte, together
When can also assign material preferable high rate performance.
The present invention provides a kind of silicon based composite material and preparation method thereof, negative material and lithium batteries.The preparation method
It is simple and practicable, safe, be easy to mass produce, the silicon based composite material that this method prepares is made after being mixed with carbon material
For negative electrode of lithium ion battery, have the advantages that cycle performance is excellent, high rate performance is good.
Description of the drawings
Hereinafter, carry out the embodiment that the present invention will be described in detail in conjunction with attached drawing, wherein：
Fig. 1 is the electron microscope that silicon based composite material is made in embodiment 1；
Fig. 2 is the capacity holding figure that silicon based composite material is made in embodiment 1；
Fig. 3 is the rate charge-discharge figure that silicon based composite material is made in embodiment 1；
Fig. 4 is the full battery capacity holding figure that silicon based composite material is made in embodiment 1；
Fig. 5 is the capacity holding figure that silicon based composite material is made in comparative example 1；
Fig. 6 is the rate charge-discharge figure that silicon based composite material is made in comparative example 1.
Specific implementation mode
With reference to embodiment, the present invention is further described in detail, but is not intended to the guarantor of the limitation present invention
Protect range.Wherein：
Commercial graphite materials A is purchased from Jiangxi Zi Chen Science and Technology Ltd.s；
Commodity soft carbon material B is purchased from Jiangxi Zi Chen Science and Technology Ltd.s.
Embodiment 1
Preparation method includes the following steps (1)-(3)：
(1) under vacuum, by silicon and silica according to molar ratio 1：1 to be heated to 1400 after evenly mixing Celsius
Degree, the natural graphite for being 600 degrees Celsius using temperature is as deposited base material according to mass ratio 1:5 deposited oxide Asia silicon；
(2) by obtained material according to mass ratio 8:2 mixed with asphalt after heat treatment 2h is carried out at 850 DEG C；
(3) material will be obtained and carry out physics except magnetic treatment.
The grain size that material is measured by Malvern laser particle analyzer measures the specific surface area of material by nitrogen adsorption methods.
The average grain diameter for obtaining material is 20 microns, specific surface area 5m2/g.The mass fraction of wherein carbon material is
70%, the mass fraction of silica-base material is 14%, and remainder is carbon coating layer, and the mass fraction of silicon is in the silica-base material
60%, oxygen 40%.
By obtained material and commercial graphite A according to mass ratio 1:1 is used as lithium ion battery negative material after evenly mixing, will
The carbon black that negative material is 2% with mass ratio, 2% cellulosic acid sodium are obtained, 3% butadiene-styrene rubber uniformly mixes in aqueous solvent
Cell size is synthesized, coated on copper foil, the square piece of 8*8mm is cut into after drying, is dried in vacuo under 110 degrees Celsius after 12h
Half-cell is assembled to lithium piece in glove box, evaluates its chemical property.
Electro-chemical test pattern is that first week 0.1C is discharged to 0.005V, and 0.05C is discharged to 0.005V, and 0.02C is discharged to
0.005V.It standing 5s and 1V cut-offs is charged to 0.1C, following cycle is that 0.5C is discharged to 0.005V, and 0.2C is discharged to 0.005V,
0.05C is discharged to 0.005V, and 0.02C is discharged to 0.005V, and charging to 1V after standing 5s with 0.5C ends.
The program of test multiplying power is that first three weeks 0.2C is discharged to 0.005V, and 0.05C is discharged to 0.005V, and 0.02C is discharged to
1V cut-offs are charged to 0.5C after 0.005V, standing 5s.Keep discharge-rate constant later, changing rate of charge successively is
0.5C,1C,2C,3C,5C,10C.It is that 0.2C is constant to keep rate of charge later, and it is 0.5C, 1C, 2C to change discharge-rate successively
It is discharged to 0.005V.Each above-mentioned multiplying power recycles five weeks, and five weeks average value is taken to evaluate its high rate performance.
Above-mentioned electric discharge is process of intercalation, corresponds to the charging in full battery, is charged as de- lithium process, corresponds to full battery
Electric discharge.
It is that anode is assembled into the soft of 1Ah with cobalt acid lithium after gained negative material is coated according to aforementioned proportion on copper foil
Packet battery tests the cycle performance under its 0.5C.
Fig. 1 is the electron microscopic picture that silicon based composite material is made in the present embodiment, it can be seen that the sub- silicon of oxidation is uniformly distributed in stone
Ink material surface.
Fig. 2 is the capacity holding figure that silicon based composite material is made in the present embodiment, it is seen that its capacity retention can be very excellent
Different (100 weeks close to 98%).
Fig. 3 is the rate charge-discharge figure that silicon based composite material is made in the present embodiment, it is seen that its capacity under high magnification is sent out
It is very excellent to wave performance, especially 5C 10C take off lithium (80%, 70%), the embedding lithiums of 1C 2C (70%, 60%).
Fig. 4 is the full battery capacity holding figure that silicon based composite material is made in the present embodiment.
Embodiment 2
The present embodiment is intended to illustrate influence of the carbon coating mode to material.
Preparation method includes the following steps (1)-(2)：
(1) under vacuum, by silicon and silica according to molar ratio 1：1 to be heated to 1400 after evenly mixing Celsius
Degree, the natural graphite for being 600 degrees Celsius using temperature is as deposited base material according to mass ratio 1:5 deposited oxide Asia silicon；Deposition is completed
It is sent into toluene into cavity according to mass ratio afterwards, while being warming up to 900 degree, keeps the temperature 2h；
(2) material will be obtained and carry out physics except magnetic treatment.
The average grain diameter for obtaining material is 20 microns, specific surface area 2m2/g.The mass fraction of wherein carbon material is
70%, the mass fraction of silica-base material is 14%, and remainder is carbon coating layer, and the mass fraction of silicon is in the silica-base material
60%, the mass fraction of oxygen is 40%.
Silicon based composite material will be obtained with commercial graphite materials A according to mass ratio 1:It is negative as lithium ion battery after 1 mixing
Pole material, according to its half-cell chemical property of test described in embodiment 1.
Embodiment 3
The present embodiment is intended to illustrate influence of the ratio for changing silicon and silica to material.
Preparation method includes the following steps (1)-(3)：
(1) under vacuum, by silicon and silica according to molar ratio 1.2：1 to be heated to 1400 after evenly mixing Celsius
Degree, the natural graphite for being 600 degrees Celsius using temperature is as deposited base material according to mass ratio 1:5 deposited oxide Asia silicon；
(2) by obtained material according to mass ratio 8:2 mixed with asphalt after heat treatment 2h is carried out at 850 DEG C；
(3) material will be obtained and carry out physics except magnetic treatment.
The average grain diameter for obtaining material is 20 microns, specific surface area 5m2/g.The mass fraction of wherein carbon material is
70%, the mass fraction of silica-base material is 14%, and remainder is carbon coating layer, and the mass fraction of silicon is in the silica-base material
65%, the mass fraction of oxygen is 35%.
Material will be obtained with commercial graphite materials A according to mass ratio 1:It is used as lithium ion battery negative material after 1 mixing, is pressed
According to its half-cell chemical property of test described in embodiment 1.
Embodiment 4
The present embodiment is intended to the influence for illustrating depositing temperature to material.
Preparation method includes the following steps (1)-(3)：
(1) under vacuum, by silicon and silica according to molar ratio 1：1 to be heated to 1400 after evenly mixing Celsius
Degree, the natural graphite for being 400 degrees Celsius using temperature is as deposited base material according to mass ratio 1:5 deposited oxide Asia silicon；
(2) by obtained material according to mass ratio 8:2 mixed with asphalt after heat treatment 2h is carried out at 850 DEG C；
(3) material will be obtained and carry out physics except magnetic treatment.
Material will be obtained with commercial graphite materials A according to mass ratio 1:It is used as lithium ion battery negative material after 1 mixing, is pressed
According to its half-cell chemical property of test described in embodiment 1.
The average grain diameter for obtaining material is 20 microns, specific surface area 6m2/g.The mass fraction of wherein carbon material is
70%, the mass fraction of silica-base material is 14%, and remainder is carbon coating layer, and the mass fraction of silicon is in the silica-base material
60%, oxygen 40%.
Embodiment 5
The present embodiment is intended to illustrate influence of the silica-base material mass ratio to material.
Preparation method includes the following steps (1)-(3)：
(1) under vacuum, by silicon and silica according to molar ratio 1：1 to be heated to 1400 after evenly mixing Celsius
Degree, the natural graphite for being 400 degrees Celsius using temperature is as deposited base material according to mass ratio 1:3 deposited oxide Asia silicon；
(2) by obtained material according to mass ratio 8:2 mixed with asphalt after heat treatment 2h is carried out at 850 DEG C；
(3) material will be obtained and carry out physics except magnetic treatment.
The average grain diameter for obtaining material is 23 microns, specific surface area 10m2/g.The mass fraction of wherein carbon material is
63%, the mass fraction of silica-base material is 21%, and remainder is carbon coating layer, and the mass fraction of silicon is in the silica-base material
60%, oxygen 40%.
Material will be obtained with commercial graphite materials A according to mass ratio 1:It is used as lithium ion battery negative material after 2 mixing, is pressed
According to its half-cell chemical property of test described in embodiment 1.
Embodiment 6
The present embodiment is intended to the influence for illustrating base material to composite material.
Preparation method includes the following steps (1)-(3)：
(1) under vacuum, by silicon and silica according to molar ratio 1：1 to be heated to 1400 after evenly mixing Celsius
Degree, the soft carbon material for being 400 degrees Celsius using temperature is as deposited base material according to mass ratio 1:5 deposited oxide Asia silicon；
(2) by obtained material according to mass ratio 8:2 mixed with asphalt after heat treatment 2h is carried out at 850 DEG C；
(3) material will be obtained and carry out physics except magnetic treatment.
The average grain diameter for obtaining material is 15 microns, specific surface area 4m2/g.The mass fraction of wherein carbon material is
70%, the mass fraction of silica-base material is 14%, and remainder is carbon coating layer, and the mass fraction of silicon is in the silica-base material
60%, oxygen 40%.
Material will be obtained with commercial graphite materials A according to mass ratio 1:It is used as lithium ion battery negative material after 1 mixing, is pressed
According to its half-cell chemical property of test described in embodiment 1.
Embodiment 7
The present embodiment is intended to influence of the explanation using modified oxidized sub- silicon to material.
Preparation method includes the following steps (1)-(3)：
(1) under vacuum, by silicon, silica, boron oxide, according to molar ratio 2:1:1 is heated to after evenly mixing
1400 degrees Celsius, the natural graphite for being 600 degrees Celsius using temperature is as deposited base material according to mass ratio 1:5 deposition silica-base materials；
(2) by obtained material according to mass ratio 8:2 mixed with asphalt after heat treatment 2h is carried out at 850 DEG C；
(3) material will be obtained and carry out physics except magnetic treatment.
The average grain diameter for obtaining material is 20 microns, specific surface area 5m2/g.The mass fraction of wherein carbon material is
70%, the mass fraction of silica-base material is 14%, and remainder is carbon coating layer, and the mass fraction of silicon is in the silica-base material
52%, the mass fraction of oxygen is 45%, and the mass fraction of boron is 3%.
Material will be obtained with commodity soft carbon material B according to mass ratio 1:It is used as lithium ion battery negative material after 1 mixing, is pressed
According to its half-cell chemical property of test described in embodiment 1.
Embodiment 8
The present embodiment is intended to influence of the explanation using modified oxidized sub- silicon to material.
Preparation method includes the following steps (1)-(3)：
(1) under vacuum, by silicon, silica, manganese-silicon, according to molar ratio 2:0.5:1 adds after evenly mixing
Heat is to 1400 degrees Celsius, and the natural graphite for being 600 degrees Celsius using temperature is as deposited base material according to mass ratio 1:3 deposition silicon substrates
Material；
(2) by obtained material according to mass ratio 8:2 mixed with asphalt after heat treatment 2h is carried out at 850 DEG C；
(3) material will be obtained and carry out physics except magnetic treatment.
The average grain diameter for obtaining material is 30 microns, specific surface area 8m2/g.The mass fraction of wherein carbon material is
63%, the mass fraction of silica-base material is 21%, and remainder is carbon coating layer, and the mass fraction of silicon is in the silica-base material
60%, the mass fraction of oxygen is 10%, and the mass fraction of boron is 30%.
Material will be obtained with commodity soft carbon material B according to mass ratio 1:It is used as lithium ion battery negative material after 2 mixing, is pressed
According to its half-cell chemical property of test described in embodiment 1.
Embodiment 9
The present embodiment is intended to influence of the explanation using modified oxidized sub- silicon to material.
Preparation method includes the following steps (1)-(3)：
(1) under vacuum, by silicon, silica, aluminium oxide, according to molar ratio 2:1:1 is heated to after evenly mixing
1400 degrees Celsius, the natural graphite for being 600 degrees Celsius using temperature is as deposited base material according to mass ratio 1:5 deposition silica-base materials；
(2) by obtained material according to mass ratio 8:2 mixed with asphalt after heat treatment 2h is carried out at 850 DEG C；
(3) material will be obtained and carry out physics except magnetic treatment.
The average grain diameter for obtaining material is 20 microns, specific surface area 6m2/g.The mass fraction of wherein carbon material is
70%, the mass fraction of silica-base material is 14%, and remainder is carbon coating layer, and the mass fraction of silicon is in the silica-base material
40%, the mass fraction of oxygen is 35%, and the mass fraction of aluminium is 25%.
Material will be obtained with commercial graphite materials A according to mass ratio 1:It is used as lithium ion battery negative material after 1 mixing, is pressed
According to its half-cell chemical property of test described in embodiment 1.
Embodiment 10
The present embodiment is intended to influence of the explanation using modified oxidized sub- silicon to material.
Preparation method includes the following steps (1)-(3)：
(1) under vacuum, by silicon, silica, metallic tin, according to molar ratio 2:1.5:0.5 adds after evenly mixing
Heat is to 1400 degrees Celsius, and the natural graphite for being 600 degrees Celsius using temperature is as deposited base material according to mass ratio 1:5 deposition silicon substrates
Material；
(2) by obtained material according to mass ratio 8:2 mixed with asphalt after heat treatment 2h is carried out at 850 DEG C；
(3) material will be obtained and carry out physics except magnetic treatment.
The average grain diameter for obtaining material is 20 microns, specific surface area 2m2/g.The mass fraction of wherein carbon material is
70%, the mass fraction of silica-base material is 14%, and remainder is carbon coating layer, and the mass fraction of silicon is in the silica-base material
48%, the mass fraction of oxygen is 23%, and the mass fraction of tin is 29%.
Material will be obtained with commercial graphite materials A according to mass ratio 1:It is used as lithium ion battery negative material after 1 mixing, is pressed
According to its half-cell chemical property of test described in embodiment 1.
Comparative example 1
Preparation method includes the following steps (1)-(6)：
(1) under vacuum, by silicon and silica according to molar ratio 1：1 to be heated to 1400 after evenly mixing Celsius
Degree, it is on 600 degrees Celsius of common stainless steel substrates to deposit to temperature；
(2) obtained oxidation Asia silicon is broken by jaw successively, coarse crushing, to 3-5 microns after air-flow crushing；
(3) the oxidation Asia silicon after crushing is crushed to about 200nm by ball mill by wet process；
(4) sub- silicon slurry will be aoxidized according to 1：1.5：5 ratio mixing asphalt and commercial graphite A, later by slurry
Drying；
(5) material obtained carries out heat treatment 2h at 850 DEG C；
(6) material will be obtained and carry out physics except magnetic treatment.
Silicon based composite material will be obtained with commercial graphite materials A according to mass ratio 1:It is negative as lithium ion battery after 1 mixing
Pole material, according to its half-cell chemical property of test described in embodiment 1.
Fig. 5 is the capacity holding figure that silicon based composite material is made in this comparative example, due to identical as 1 ratio of embodiment, appearance
Amount is close, but 100 weeks capacity retention ratios only have 92%.
Fig. 6 is the rate charge-discharge figure that silicon based composite material is made in this comparative example, it is seen that its capacity under high magnification is sent out
It is particularly poor to wave performance, especially 5C 10C take off lithium (70%, 25%), the embedding lithiums of 1C 2C (60%, 20%).
Comparative example 2
This comparative example is intended to illustrate the material horizontal of prior art preparation
Preparation process includes as follows：
(1) under vacuum, by silicon and silica according to molar ratio 1：1 to be heated to 1400 after evenly mixing Celsius
Degree, it is on 600 degrees Celsius of common stainless steel substrates to deposit to temperature；
(2) obtained oxidation Asia silicon is broken by jaw successively, coarse crushing, to 3-5 microns after air-flow crushing；
(3) by oxidation Asia silicon and the asphalt after crushing according to 1：Hot place is carried out at 850 DEG C after 1.5 ratio mixing
Manage 2h.
(4) material will be obtained and carry out physics except magnetic treatment.
Silicon based composite material will be obtained with commercial graphite materials A according to mass ratio 1:It is negative as lithium ion battery after 5 mixing
Pole material, according to its half-cell chemical property of test described in embodiment 1.
Show that silicon based composite material made from embodiment 1-8 is compared as the chemical property of negative material in the following table 1.
Table 1
The universal first effect of silicon based composite material obtained using preparation method of the present invention it can be seen from the result of table 1
Higher, cycle is preferable.It can be seen that from the comparison of each embodiment when carrying out gas phase cladding using toluene, on the one hand further
Preparation flow is simplified, another party kept man of a noblewoman's effect slightly reduces, this may be due to being mixed into a small amount of air in operation, making system
It is standby go out caused by the sub- silicon of oxidation aoxidized；Improving silicon and proportion of silica makes the capacity of material and first effect improve, but cycle performance
It is declined slightly；Reducing depositing temperature keeps the metastable degree of material higher, is oxidized easily, and causes first effect relatively relatively low；Improve silicon
The ratio of sill influences the performance of material little；Deposition materials head effects are relatively low to cause integral material head effects relatively low；Selection changes
The oxidation Asia silicon of property can be obviously improved first effect；And the flow of comparative example 1 is complicated, and aoxidize and roll into a ball in the process material of nanosizing
It is poly- serious, therefore the material head effects prepared are very low, cycle is poor.Comparative example 2 uses the prior art, although flow is simple,
It is that sub- silicon is aoxidized using micron, causes the cycle of material very poor.
Claims (13)
1. a kind of preparation method of silicon based composite material, includes the following steps：
(1) silica-base material is deposited in the surface homogenous gas-phase of carbon material；
(2) carbon coating is carried out to step (1) resulting materials；
(3) physics is carried out to step (2) resulting materials and removes magnetic treatment.
2. preparation method according to claim 1, wherein the silica-base material is sub- by silicon and silica, and/or oxidation
Silicon, and optional one kind in B, Al, Na, Mg, Ca, Ba, Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ge, Sn or
Several complex elements or its oxide are compounded to form；Preferably, the step (1) is under vacuum, by silicon and two
Silica, and/or the sub- silicon of oxidation, and it is optional selected from B, Al, Na, Mg, Ca, Ba, Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr,
The complex element of one or more of Mo, Ge, Sn or its oxide are heated to 1000-2000 degrees Celsius after mixing,
It is preferred that 1000~1600 degrees Celsius, it is deposited on the carbon material that temperature is 200-700 degrees Celsius.
3. preparation method according to claim 1, wherein the step (2) carries out carbon-coated mode and is selected from：
1) it in vapor deposition processes, is passed through one or more in gaseous carbon sources, is carbonized under 700-1100 degrees Celsius；Or
2) after vapor deposition, by obtained material and liquid after either solid carbon source is mixed by solid phase or even in liquid phase,
It is heat-treated under 700-1100 degrees Celsius.
4. preparation method according to claim 1, wherein in the silicon based composite material, the mass fraction of carbon material
Mass fraction for 10%-90%, silica-base material is 1-80%, and the mass fraction of carbon coating layer is 5%-30%；Preferably, institute
The mass fraction for stating element silicon in silica-base material is 40%-80%, and the mass fraction of oxygen element is 10%-60%；Complex element
Mass fraction be 0%-40%.
5. preparation method according to claim 1, wherein the carbon material be selected from soft carbon, hard carbon, carbonaceous mesophase spherules,
The group of one or more of graphitized intermediate-phase carbosphere, natural graphite, modified natural graphite, artificial graphite and porous graphite
It closes；Preferably, the average grain diameter of the carbon material is 1-40 microns.
6. preparation method according to claim 1, wherein the microstructure of the silica-base material is the silicon crystallite of 1-50nm
Or silicon-base alloy crystallite Dispersed precipitate is among metal oxide and/or composite oxides parent phase.
7. preparation method according to claim 1, wherein the silica-base material by silicon and silica mixture shape
At wherein the molar ratio of silicon and silica is 1:2~2:1.
8. preparation method according to claim 1, wherein the step (1) has been deposited 20- on the carbon material
The sub- silicon of the oxidation of 2000nm or the modified oxidized sub- particle of silicon or the material of film；Preferably, the carbon material is graphite.
9. preparation method according to claim 3, wherein the mode 1 of the step (2)) in, the gaseous carbon sources being passed through are
It is one or more in toluene, methane and acetylene；
The mode 2 of the step (2)) in, the liquid or solid carbon source are sugar, pitch or polymer precursor；Preferably,
The sugar is glucose, and the pitch is asphalt or mesophase pitch, and the polymer precursor is phenolic resin or gathers
Acrylonitrile.
10. preparation method according to any one of claim 1 to 9, wherein the ratio table for the material that the step (2) obtains
Area is 2-20m2/ g, average grain diameter are 2-40 μm, and shape is spherical shape, elliposoidal, cobble shaped and/or random polygon
Shape；And/or
When the silicon based composite material is as lithium ion battery negative material, charge specific capacity 400-1500mAh/g.
11. silicon based composite material prepared by method according to any one of claim 1 to 10, specific surface area 2-
20m2/ g, average grain diameter are 2-40 μm, and shape is spherical shape, elliposoidal, cobble shaped and/or random polygon.
12. a kind of lithium ion battery negative material, the silicon substrate prepared by method according to any one of claim 1 to 10
Silicon based composite material described in composite material or claim 11 and carbon material composition, it is preferable that the silicon based composite material exists
Mass percent in the lithium ion battery negative material is more than 2%；Preferably, the carbon material include soft carbon, hard carbon, in
Between one or more of phase carbosphere, graphitized intermediate-phase carbosphere, natural graphite, modified natural graphite and artificial graphite
Combination.
13. a kind of lithium battery includes the silicon based composite material prepared by method according to any one of claim 1 to 10
Or the silicon based composite material described in claim 11 or the lithium ion battery negative material described in claim 12.
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