CN108963194A - A kind of silicon based composite material and its preparation method and application - Google Patents
A kind of silicon based composite material and its preparation method and application Download PDFInfo
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- CN108963194A CN108963194A CN201710350431.4A CN201710350431A CN108963194A CN 108963194 A CN108963194 A CN 108963194A CN 201710350431 A CN201710350431 A CN 201710350431A CN 108963194 A CN108963194 A CN 108963194A
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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
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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
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- 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
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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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- 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 material, general formula SiAxOy, wherein A is one of B, Al, Na, Mg, Ca, Ba, Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ge, Sn or a variety of, and wherein x is greater than 0.001 and less than 10, y greater than 0.1 and less than 10.Negative electrode material the present invention also provides the preparation method of the silicon based composite material and comprising the silicon based composite material, battery and lithium-ion capacitor.High rate performance and its first effect greatly improved while improving cycle performance in silicon based composite material of the invention.It include that negative electrode material and lithium ion battery, lithium-ion capacitor of silicon based composite material of the invention etc. equally have the characteristics that high-energy density, high circulation performance, high rate capability, high first effect.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of silicon based composite material and its preparation method and application.
Background technique
Lithium ion battery has gradually been occupied with mobile phone, computer etc. is representative since last century, the nineties emerged for the first time
Portable consumer electronics market, in extensive energy storage, electric car field also has broad application prospects.Negative electrode of lithium ion battery
Coke class of the material since most gradually develops natural graphite by now, and the technology of artificial graphite etc., carbon based negative electrodes is non-
It is often mature, however, the theoretical specific capacity of 372mAh/g is no longer satisfied people's requirement growing to energy density, exploitation
Novel anode material has become the most important thing.
The advantages that theoretical specific capacity of silicon materials is up to 4200mAh/g, and has voltage low again, resourceful, it is considered to be
Next-generation lithium ion battery negative material.However, silicon huge bulk strain in cyclic process has very greatly its cycle performance
Influence, on this basis, Chinese patent application CN1513922A and CN102460784A disclose micro- by the silicon of Nano grade
The oxidation Asia silicon that brilliant Dispersed precipitate is constituted in silica matrices shows good cycle performance, receives the favor of people.
However, the silica aoxidized in sub- silicon is not effectively reversible removal lithium embedded, cause all efficiency of the head for aoxidizing sub- silicon generally relatively low,
And the silicate poorly conductive that its embedding lithium is formed, cause the high rate performance for aoxidizing sub- silicon also poor.To solve the above problems, in
In state patent application CN103022446A, CN104022257A, CN103872303A and CN103779547A, people are attempted to oxygen
Change sub- silicon and carry out different surface treatment and doping treatment, achieves certain effect, however there is no change to aoxidize sub- silicon
Microstructure and composition, the above problem still remain.
Summary of the invention
Therefore, it is an object of the invention to the head for silica itself to imitate low, the disadvantage of high rate performance difference, by material
Microstructure and composition set out, a kind of silicon based composite material and the negative electrode material comprising the silicon based composite material are provided.Include
The negative electrode material of silicon based composite material of the invention has the features such as first charge discharge efficiency is high, and cycle performance is excellent, good rate capability, and
Preparation method is simple, is easy to be mass produced.
It is a further object to provide a kind of methods for preparing silicon based composite material of the invention.
A further object of the present invention is to provide a kind of negative electrode material comprising silicon based composite material of the invention.
It is also another object of the present invention to provide a kind of comprising silicon based composite material of the invention or cathode material of the invention
The battery or lithium-ion capacitor of material.
It is a further object to provide the purposes of negative electrode material of the present invention.
Unless otherwise stated, heretofore described XRD diffraction maximum be obtained using Cu-K α actinometry, with 2 angles θ
Spend the characteristic peak indicated.Its precision is ± 0.2 degree.
The purpose of the present invention is achieved through the following technical solutions.
On the one hand, the present invention provides a kind of silicon based composite material, general formula SiAxOy, wherein A be B, Al, Na, Mg, Ca,
One of Ba, Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ge, Sn or a variety of, wherein x is greater than 0.001 and big less than 10, y
In 0.1 and less than 10.
Preferably, wherein the microstructure of the silicon based composite material is multiphase Dispersed precipitate, the silicon based composite material
Including at least a kind of metal phase, a kind of metal oxide phase and/or composite oxides phase；It is highly preferred that the wherein metal phase
Content be the silicon based composite material gross mass 20%-90%, more preferably 30%-60%；The metal oxide phase
And/or the content of composite oxides phase is the 20%-90%, more preferably 30%-60% of the silicon based composite material gross mass.
Preferably, wherein the size of the metal phase is 0.5-100nm；It is highly preferred that the metal phase by Si and B, Al,
One of Na, Mg, Ca, Ba, Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ge, Sn or a variety of simple substance or composition of alloy.
Preferably, wherein the metal phase is evenly distributed on one or more metal oxide phases and/or composite oxides
Xiang Zhong；It is highly preferred that the metal oxide be mutually Si, B, Al, Na, Mg, Ca, Ba, Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr,
One of Mo, Ge, Sn or a variety of oxides, the composite oxides be mutually Si, B, Al, Na, Mg, Ca, Ba, Ti, Mn,
One of Fe, Co, Ni, Cu, Zn, Zr, Mo, Ge, Sn or a variety of composite oxides.
Preferably, the B element in the material by boron oxide, borosilicate alloy or with other elements compoundings in a manner of exist,
The highest peak of the corresponding XRD diffraction maximum of the boron oxide is located at 27.8 degree, and the corresponding XRD diffraction maximum of the borosilicate alloy is most
Strong peak is located at 33.4 degree.
Preferably, the Al element in the material by aluminium oxide, alumina silicate or with other elements compoundings in a manner of exist,
The highest peak of the corresponding XRD diffraction maximum of the aluminium oxide is located at 42.7 degree, the corresponding XRD diffraction maximum of the alumina silicate it is most strong
Peak is located at 26.6 degree and/or 26.2 degree.
Preferably, the Na element in the material by sodium metasilicate or with other elements compoundings in a manner of exist, the silicon
Sour sodium is Na2(Si3O7)、Na2(Si2O5) and Na (SiO3) one of or a variety of mixing.
Preferably, the Mg element in the material by magnesia, magnesium silicate or with other elements compoundings in a manner of exist,
The highest peak of the corresponding XRD diffraction maximum of the magnesia is located at 42.9 degree, and the magnesium silicate is MgSiO3、Mg2SiO4With
Mg2Si2O6One of or a variety of mixing, wherein Mg2SiO4Corresponding XRD has a pair of of characteristic peak at 37.3 degree and 38.4 degree.
Preferably, the Ca element in the material by calcium oxide, calcium silicates or with other elements compoundings in a manner of exist,
The highest peak of the corresponding XRD diffraction maximum of the calcium oxide is located at 37.4 degree, and the calcium silicates is CaSiO3、CaSi2O5、
Ca2SiO4And Ca3Si3O9One of or a variety of mixing.
Preferably, the Ba element in the material by barium monoxide, barium silicate or with other elements compoundings in a manner of exist,
The highest peak of the corresponding XRD diffraction maximum of the barium monoxide is located at 28.1 degree, and the barium silicate is BaSiO3、BaSi2O5、
Ba2SiO4、Ba4Si6O16And Ba6Si10O26One of or a variety of mixing.
Preferably, the Ti element in the material by titanium oxide, titanium silicon or with other elements compoundings in a manner of deposit
It is TiO in, the titanium oxide2、Ti2O3And Ti3O5Deng one or more of mixtures, the titanium silicon is TiSi2、Ti5Si4、
Ti5Si3With the combination of one or more of TiSi, corresponding to XRD has feature at 40.4,37.2,40.8 and 36.9 degree respectively
Peak.
Preferably, the Mn element in the material with manganese oxide, manganese-silicon, manganous silicate or with other elements compoundings
Mode exists, and the manganese oxide is MnO2、Mn3O4And Mn2O3One or more of mixing, the manganese-silicon be Mn3Si、
MnSi and Mn5Si2One or more of mixing, correspond to XRD have characteristic peak at 44.8,44.4 and 43.1 degree respectively, institute
Stating manganous silicate is MnSiO3, corresponding to XRD has characteristic peak at 32.5 degree.
Preferably, the Fe element in the material with iron oxide, ferro-silicium, ferrosilite or with other elements compoundings
Mode exists, and the iron oxide is Fe2O3, correspond to XRD has characteristic peak at 33.2 degree, and the ferro-silicium is FeSi2And/or
FeSi, corresponding XRD have characteristic peak at 17.3,45.0 degree respectively, and the ferrosilite is FeSiO3And/or Fe2SiO4。
Preferably, the Co element in the material with cobalt oxide, cobalt silicon alloy, cobaltous silicate or with other elements compounding sides
Formula exists, and the cobalt oxide is Co3O4And/or CoO, corresponding XRD have characteristic peak, the cobalt silicon at 36.8,42.4 degree respectively
Alloy is CoSi, Co2Si and CoSi2One or more of mixing, corresponding XRD is respectively at 45.7,45.3 and 47.9 degree
There is characteristic peak, the cobaltous silicate is CoSiO3And/or Co2SiO4。
Preferably, the Ni element in the material with nickel oxide, nickel silicon alloy, silicic acid nickel or with other elements compoundings
Mode exists, and the nickel oxide is NiO and/or NiO2, corresponding XRD has characteristic peak, the nickel at 43.3,18.6 degree respectively
Silicon alloy is NiSi, Ni2Si、Ni3Si2And Ni3One of Si or several mixing, corresponding XRD respectively 47.2,
46.2, there is characteristic peak at 45.0 and 44.7 degree, the silicic acid nickel is Ni2SiO4。
Preferably, the Cu element in the material by cupro silicon, silicic acid ketone or with other elements compoundings in a manner of deposit
It is Cu in, the cupro silicon9Si、Cu5Si、Cu6.6Si、Cu15Si4And Cu3One of Si or several mixing, it is corresponding
XRD has characteristic peak at 43.3,43.7,43.2,44.1,45.0 degree respectively, and the silicic acid ketone is CuSiO3, corresponding XRD exists
There is characteristic peak at 28.0 degree.
Preferably, the Zn element in the material by zinc oxide, zinc silicate or with other elements compoundings in a manner of exist,
The zinc oxide is ZnO and/or ZnO2, corresponding XRD has characteristic peak at 42.3,37.0 degree respectively；The zinc silicate is
ZnSiO3And/or Zn2SiO4。
Preferably, the Zr element in the material by zirconium silicon alloy, zirconium silicate or with other elements compoundings in a manner of deposit
It is Zr in, the zirconium silicon alloy2Si、Zr5Si3、ZrSi2、Zr5Si4And Zr3Si2The mixing of middle one or more, the zirconium silicate
For ZrSiO4, XRD has characteristic peak at 27.0 degree.
Preferably, the Mo element in the material by molybdenum-silicon alloy or with other elements compoundings in a manner of exist, it is described
Molybdenum-silicon alloy is MoSi2、Mo5Si3And Mo3One of Si or mixing.
Preferably, the Ge element in the material with the GeSi alloy of arbitrary proportion, germanium oxide or with other elements
Complex method exists, and the germanium oxide is GeO2, XRD has characteristic peak at 26.4 degree.
Preferably, the Sn element in the material by tin oxide, metallic tin or with other elements compoundings in a manner of deposit
It is SnO in, the tin oxide2And/or SnO, corresponding XRD have characteristic peak at 26.5 degree, 29.9 degree respectively；The metallic tin is
Simple substance Sn, corresponding XRD have characteristic peak at 30.6 degree.
Preferably, wherein the average grain diameter of the silicon based composite material is 50 nanometers~40 microns；Preferably, the silicon substrate
The average grain diameter of composite material is 1 micron~10 microns.
Preferably, wherein the silicon based composite material as negative electrode material charge specific capacity be 400-2500mAh/g.
Silicon based composite material of the invention can be used for lithium ion battery, lithium-sulfur cell, all-solid-state battery or lithium-ion electric
Container etc..
Preferably, silicon based composite material of the present invention is prepared by a step vapour deposition process or two-step method；Institute
A step vapour deposition process is stated the following steps are included: by elemental silicon, one or both of the oxide and optional oxygen of simple substance A and A
SiClx in elemental mole ratios Si:A:O=1:x:y ratio mixing after through beam bombardment, magnetron sputtering, electrical induction, electricity
The modes such as resistance heating deposit after being evaporated to gas, crush later, obtain the silicon based composite material；The two-step method includes following
Step: add after first mixing elemental silicon and silica in proportion through beam bombardment, magnetron sputtering, electrical induction, resistance
The modes such as heat are deposited as aoxidizing sub- silicon after being evaporated to gas, carry out after evenly mixing with the oxide of simple substance A and/or A again later
Heat treatment, obtains the silicon based composite material.
On the other hand, the present invention provides a kind of method for preparing silicon based composite material of the present invention, is a step gas
Phase sedimentation or two-step method, in which:
The one step vapour deposition process the following steps are included: by one or both of elemental silicon, the oxide of simple substance A and A, with
And optional silica in elemental mole ratios Si:A:O=1:x:y ratio mix after through beam bombardment, magnetron sputtering, inductance
Should heat, resistance heating to the modes such as 800-1800 DEG C is evaporated to and is deposited on temperature after gas and is on 50-800 DEG C of substrate, it
Deposit is broken for powder afterwards, obtains the silicon based composite material；
The two-step method the following steps are included: after elemental silicon and silica are mixed in proportion first through beam bombardment,
The modes such as magnetron sputtering, electrical induction, resistance heating are deposited as aoxidizing sub- silicon after being evaporated to gas, later with simple substance A and/or
The oxide of A carries out heat treatment 2-24h at 600-1500 DEG C after evenly mixing, obtains the silicon based composite material.
Preferably, the simple substance A is in B, Al, Na, Mg, Ca, Ba, Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ge, Sn
Any one or a variety of simple substance element or intermetallic compound.
Another aspect, the present invention provide a kind of negative electrode material, and it includes silicon based composite material of the present invention and carbon materials
Material, wherein the content of the silicon based composite material is 2% or more of the negative electrode material gross mass；The carbon material includes soft
One in carbon, hard carbon, carbonaceous mesophase spherules, graphitized intermediate-phase carbosphere, natural graphite, modified natural graphite and artificial graphite
Kind or several combinations；Preferably, carbon coating processing is carried out to the silicon based composite material.
In another aspect, the present invention provides a kind of battery, it includes silicon based composite material of the present invention or institutes of the present invention
The negative electrode material stated；Preferably, the battery is lithium ion battery, lithium-sulfur cell or all-solid-state battery etc..
On the other hand, the present invention provides a kind of lithium-ion capacitor, it includes silicon based composite material of the present invention or
Negative electrode material of the present invention.
Another aspect, the present invention provides the purposes of negative electrode material of the present invention, be used for as lithium ion battery,
The negative electrode material or part of it of lithium-ion capacitor, lithium-sulfur cell, all-solid-state battery etc..
The silicon based composite material of the invention oxidation Asia silicon more mature based on current technology, to its microstructure and form into
High rate performance and its first effect greatly improved while improving cycle performance in the change of row fundamentally.The present invention also public affairs simultaneously
The preparation method of the silicon based composite material is opened, which has the characteristics that be simple and efficient, and is easy to be mass produced.Packet
Negative electrode material and lithium ion battery, lithium-ion capacitor containing the composite material etc. equally have high-energy density, high circulation
The characteristics of performance, high rate capability, high first effect.
Detailed description of the invention
Hereinafter, carrying out the embodiment that the present invention will be described in detail in conjunction with attached drawing, in which:
Fig. 1 is the XRD diagram of resulting materials in the embodiment of the present invention 1；
Fig. 2 is the circulation figure of 1 resulting materials of the embodiment of the present invention；
Fig. 3 is the multiplying power figure of 1 resulting materials of the embodiment of the present invention；
Fig. 4 is the XRD diagram of 2 resulting materials of the embodiment of the present invention；
Fig. 5 is the XRD diagram of 3 resulting materials of the embodiment of the present invention；
Fig. 6 is the XRD diagram of 4 resulting materials of the embodiment of the present invention；
Fig. 7 is the XRD diagram of 5 resulting materials of the embodiment of the present invention；
Fig. 8 is the XRD diagram of 7 resulting materials of the embodiment of the present invention；
Fig. 9 is the XRD diagram of 8 resulting materials of the embodiment of the present invention；
Figure 10 is the XRD diagram of 1 resulting materials of comparative example；
Figure 11 is the circulation figure of 1 resulting materials of comparative example；
Figure 12 is the multiplying power figure of 1 resulting materials of comparative example.
Specific embodiment
The present invention will be further described combined with specific embodiments below, following embodiments be merely to illustrate the present invention and
Not limitation of the present invention.
Element can be divided into (B), (Al Na Mg Ca Ba Zn), (Ti Mn Fe Co according to the object phase composition of product
Ni Cu Zr Mo) and (Ge Sn) four classes.
Embodiment 1
Present embodiments provide a kind of preparation method of specific silicium cathode material, comprising:
(1) by metallic silicon power, boron oxide powder, SiO 2 powder adds after mixing according to molar ratio 2:1:1 into resistance
In the vacuum drying oven of heat, it is evacuated to 100Pa first, then begins to be warming up to 1400 degree, collects gas, substrate in low-temperature substrate area
Temperature is 500 degree.After reaction, obtained block is passed through into jaw crusher, boulder crusher, airslide disintegrating mill is machined to by road
Median is the powder of 3 microns (laser particle analyzer test, similarly hereinafter), and obtaining chemical formula of the invention is SiB0.5O1.25Silicon
Based composites.
(2) above-mentioned composite material and pitch are heat-treated after evenly mixing with 90:10 mass ratio, obtained material with
Artificial graphite is mixed with the ratio of mass ratio 1:5, obtains negative electrode material of the present invention.
The carbon black for being 2% by above-mentioned negative electrode material and mass ratio, 2% cellulosic acid sodium, 3% butadiene-styrene rubber is water-soluble
It is uniformly mixed into cell size in agent, coated on copper foil, the square piece of 8*8mm is cut into after drying, it is dry in 110 degrees Celsius of lower vacuum
Half-cell is assembled in glove box after dry 12h, evaluates its chemical property.
Electro-chemical test mode 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-off 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, charges to 1V after standing 5s with 0.5C and end.
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-off is charged to 0.5C after 0.005V, standing 5s.Keep discharge-rate constant later, successively changing rate of charge is
0.5C,1C,2C,3C,5C,10C.Keeping rate of charge later is that 0.2C is constant, and successively changing discharge-rate is 0.5C, 1C, 2C
It is discharged to 0.005V.Above-mentioned every kind of multiplying power recycles five weeks, takes five weeks average value to evaluate its high rate performance, the results are shown in Table 1.
XRD experiment of the present invention carries out on Bruke D8Advance (being purchased from Bruke company), uses Cu-K α spoke
It penetrates, 2 θ angular ranges of scanning are 10-90 degree.Similarly hereinafter.
The XRD spectrum of the present embodiment resulting materials is shown in Fig. 1, there is the characteristic peak of silicon at 28.5 degree, has boron oxide at 27.8 degree
Characteristic peak.
By refine from XRD spectrum, metal phase in silicon based composite material of the present invention can be released after fitting
Size is about 5nm, and the content of metal phase is about the 35% of the silicon based composite material gross mass, and the content of metal oxide phase is about
It is the 65% of the silicon based composite material gross mass.
The circulation figure and multiplying power figure of the present embodiment resulting materials are shown in Fig. 2, Fig. 3.It can be seen that the present embodiment obtains the circulation of material
Functional, high rate performance is good.
Embodiment 2
Present embodiments provide a kind of preparation method of specific silicium cathode material, comprising:
(1) by metallic silicon power, titanium dioxide powder, SiO 2 powder adds after mixing according to molar ratio 2:1:1 into resistance
In the vacuum drying oven of heat, it is evacuated to 100Pa first, then begins to be warming up to 1400 degree, collects gas, substrate in low-temperature substrate area
Temperature is 500 degree.After reaction, obtained block is passed through into jaw crusher, boulder crusher, airslide disintegrating mill is machined to by road
The powder that median is 3 microns, obtaining chemical formula of the invention is SiTi0.33O1.33Silicon based composite material.
(2) above-mentioned composite material and pitch are heat-treated after evenly mixing with 95:5 mass ratio, obtained material with
Artificial graphite is mixed with the ratio of mass ratio 1:5, obtains negative electrode material of the present invention.
Obtained negative electrode material tests its chemical property according to step described in embodiment 1, the results are shown in Table 1.
The XRD spectrum of the present embodiment resulting materials is shown in Fig. 4, in figure high-visible material by silicon (main peak be located at 28.5 degree),
Silica (main peak is located at 21.76 degree), titanium silicon (main peak is located at 40.8 degree) composition, wherein titanium silicon is Ti5Si3。
By refine from XRD spectrum, the size of metal phase in silica-base material of the present invention can be released after fitting
About 20nm, the content of metal phase are about the 40% of the silicon based composite material gross mass, and the content of metal oxide phase is about
The 60% of the silicon based composite material gross mass.
Embodiment 3
Present embodiments provide a kind of preparation method of specific silicium cathode material, comprising:
(1) by metallic silicon power, alumina powder, silicon oxide powder enters induction heating after mixing according to molar ratio 2:1:1
Vacuum drying oven in, be evacuated to 100Pa first, then begin to be warming up to 1700 degree, low-temperature substrate area collect gas, substrate temperature
Degree is 500 degree.After reaction, obtained block is passed through into jaw crusher, boulder crusher, during airslide disintegrating mill is machined to by road
The powder that position partial size is 3 microns, obtaining chemical formula of the invention is SiAl0.67O1.67Silicon based composite material.
(2) above-mentioned composite material and pitch are heat-treated after evenly mixing with 95:5 mass ratio, obtained material with
Artificial graphite is mixed with the ratio of mass ratio 1:5, obtains negative electrode material of the present invention.
Obtained negative electrode material tests its chemical property according to step described in embodiment 1, the results are shown in Table 1.
The XRD spectrum of the present embodiment resulting materials is shown in Fig. 5, in figure high-visible material by silicon (main peak be located at 28.5 degree),
Silica (is located at 20 degree of amorphous packets), aluminium oxide (main peak is located at 42.7 degree), alumina silicate (main peak is located at 26.6 degree) composition.
By refine from XRD spectrum, the size of metal phase in silica-base material of the present invention can be released after fitting
About 15nm, the content of metal phase are about the 30% of the silicon based composite material gross mass, and the content of metal oxide phase sum is about
It is the 30% of the silicon based composite material gross mass, the content of composite oxides phase is the silicon based composite material gross mass
40%
Embodiment 4
Present embodiments provide a kind of preparation method of specific silicium cathode material, comprising:
(1) after metallic silicon power, cupro silicon powder, silica being mixed according to molar ratio 2:2:1 after beam bombardment
It is deposited on the substrate that temperature is 200 degree.After reaction, obtained block is passed through into jaw crusher, boulder crusher, air-flow powder
The road Sui Jizhu is machined to the powder that median is 3 microns, and obtaining chemical formula of the invention is SiCu1.25O0.4Silicon substrate it is compound
Material.
(2) above-mentioned composite material and phenolic resin are heat-treated after evenly mixing with 95:5 mass ratio, obtained material
Material is mixed with natural graphite with the ratio of mass ratio 1:5, obtains negative electrode material of the present invention.
Obtained negative electrode material tests its chemical property according to step described in embodiment 1, the results are shown in Table 1.
The XRD spectrum of the present embodiment resulting materials is shown in Fig. 6, in figure high-visible material by silicon (main peak be located at 28.5 degree),
Silica (is located at 20 degree of amorphous packets), cupro silicon (Cu3Si, positioned at 44.5 degree of time strong peak and 45.0 highest peak) composition.
By refine from XRD spectrum, the size of metal phase in silica-base material of the present invention can be released after fitting
About 40nm, the content of metal phase are about the 80% of the silicon based composite material gross mass, and the content of metal oxide phase is about
The 20% of the silicon based composite material gross mass.
Embodiment 5
Present embodiments provide a kind of preparation method of specific silicium cathode material, comprising:
(1) enter in the vacuum drying oven of induction heating after mixing metallic silicon according to molar ratio 1.5:1 with silica, take out first
Vacuum then begins to keep the temperature after being warming up to 1400 degree, collects gas in low-temperature substrate area, underlayer temperature is 500 degree to 100Pa.
After reaction, obtained block is passed through into jaw crusher, boulder crusher, it is 3 that airslide disintegrating mill, which is machined to median by road,
The powder of micron, obtains aoxidizing sub- Si powder；
(2) it is heat-treated at 900 DEG C after mixing obtained oxidation Asia Si powder with copper oxide according to molar ratio 1:1.5
6h, obtaining chemical formula of the invention is SiCuO1.67Silicon based composite material.
(3) above-mentioned composite material and glucose are heat-treated after evenly mixing with 90:10 mass ratio, obtained material
It is mixed with graphitized intermediate-phase carbosphere with the ratio of mass ratio 1:5, obtains negative electrode material of the present invention.
Obtained negative electrode material tests its chemical property according to step described in embodiment 1, the results are shown in Table 1.
The XRD for the silicon based composite material that the present embodiment obtains is shown in Fig. 7.It can be seen that its essential characteristic is identical as above-described embodiment 5,
Only silica amount significantly improves, and cupro silicon phase content is obviously less.
By refine, the size that metal phase in silica-base material of the present invention can be released after fitting is about 25nm, gold
The content of symbolic animal of the birth year is about the 60% of the silicon based composite material gross mass, and the content of metal oxide phase is about that the silicon substrate is compound
The 40% of material gross mass.
Embodiment 6
Present embodiments provide a kind of preparation method of specific silicium cathode material, comprising:
(1) enter in the vacuum drying oven of induction heating after mixing metallic silicon according to molar ratio 1.05:1 with silica, first
It is evacuated to 100Pa, then begins to keep the temperature after being warming up to 1400 degree, collects gas, underlayer temperature 400 in low-temperature substrate area
Degree.After reaction, obtained block is passed through into jaw crusher, boulder crusher, airslide disintegrating mill is machined to median by road
For 3 microns of powder, obtain aoxidizing sub- Si powder；
(2) it is heat-treated at 1100 DEG C after mixing obtained oxidation Asia Si powder with Titanium according to molar ratio 2:1
12h, obtaining chemical formula of the invention is SiTi0.5O silicon based composite material.
(3) above-mentioned composite material and asphalt are heat-treated after evenly mixing with 95:5 mass ratio, obtained material
Material is mixed with graphitized intermediate-phase carbosphere with the ratio of mass ratio 1:5, obtains negative electrode material of the present invention.
Obtained negative electrode material tests its chemical property according to step described in embodiment 1, the results are shown in Table 1.
The size of metal phase is about 20nm in silica-base material of the present invention, and the content of metal phase is about that the silicon substrate is multiple
The 55% of condensation material gross mass, the content of metal oxide phase are about the 45% of the silicon based composite material gross mass.
Embodiment 7
Present embodiments provide a kind of preparation method of specific silicium cathode material, comprising:
(1) enter the vacuum of resistance heating after mixing metallic silicon, silica, tin oxide according to molar ratio 1:0.9:0.1
In furnace, it is evacuated to 100Pa first, then begins to keep the temperature after being warming up to 1400 degree, collects gas, substrate temperature in low-temperature substrate area
Degree is 400 degree.After reaction, obtained block is passed through into jaw crusher, boulder crusher, during airslide disintegrating mill is machined to by road
The powder that position partial size is 3 microns, obtaining chemical formula of the invention is SiSn0.1The silicon based composite material of O.
(2) above-mentioned composite material and pitch are heat-treated after evenly mixing with 95:5 mass ratio, obtained material with
Artificial graphite is mixed with the ratio of mass ratio 1:5, obtains negative electrode material of the present invention.
Obtained negative electrode material tests its chemical property according to step described in embodiment 1, the results are shown in Table 1.
The XRD spectrum of silicon based composite material obtained by the present embodiment is shown in Fig. 8, and high-visible material is by silicon (main peak position in map
In 28.5 degree), silica (is located at 20 degree of amorphous packets), metallic tin (main peak is located at 30.6 degree) composition.
By refine, the size that metal phase in silica-base material of the present invention can be released after fitting is about 30nm, gold
The content of symbolic animal of the birth year is about the 45% of the silicon based composite material gross mass, and the content of metal oxide phase is about that the silicon substrate is compound
The 55% of material gross mass.
Embodiment 8
Present embodiments provide a kind of comparison for changing metal Theil indices, comprising:
(1) enter the vacuum of resistance heating after mixing metallic silicon, silica, tin oxide according to molar ratio 1:0.5:0.5
In furnace, it is evacuated to 100Pa first, then begins to keep the temperature after being warming up to 1400 degree, collects gas, substrate temperature in low-temperature substrate area
Degree is 400 degree.After reaction, obtained block is passed through into jaw crusher, boulder crusher, during airslide disintegrating mill is machined to by road
The powder that position partial size is 3 microns, obtaining chemical formula of the invention is SiSn0.5The silicon based composite material of O.
(2) above-mentioned composite material and pitch are heat-treated after evenly mixing with 95:5 mass ratio, obtained material with
Artificial graphite is mixed with the ratio of mass ratio 1:5, obtains negative electrode material of the present invention.
Obtained negative electrode material tests its chemical property according to step described in embodiment 1, the results are shown in Table 1.
The XRD spectrum of silicon based composite material obtained by the present embodiment is shown in Fig. 9, and high-visible material is by silicon (main peak position in map
In 28.5 degree), silica (is located at 20 degree of amorphous packets), metallic tin (main peak is located at 30.6 degree) composition.The content of metallic tin is into one
Step is promoted.
By refine, the size that metal phase in silica-base material of the present invention can be released after fitting is about 35nm, gold
The content of symbolic animal of the birth year is about the 70% of the silicon based composite material gross mass, and the content of metal oxide phase is about that the silicon substrate is compound
The 30% of material gross mass.
Comparative example 1
This comparative example provides a kind of preparation method of the high magnification silicon based composite material under the prior art, comprising:
(1) enter in the vacuum drying oven of resistance heating after mixing metallic silicon according to molar ratio 1:1 with silica, take out first true
Sky then begins to keep the temperature after being warming up to 1400 degree, collects gas in low-temperature substrate area, underlayer temperature is 400 degree to 100Pa.Instead
After answering, obtained block is passed through into jaw crusher, boulder crusher, it is 3 micro- that airslide disintegrating mill, which is machined to median by road,
The powder of rice obtains the oxidation Asia Si powder that chemical formula is SiO；
(2) above-mentioned oxidation Asia Si powder and asphalt are heat-treated after evenly mixing with 95:5 mass ratio, are obtained
Material and artificial graphite mixed with the ratio of mass ratio 1:5, obtain negative electrode material described in this comparative example.
Obtained negative electrode material tests its chemical property according to step described in embodiment 1, the results are shown in Table 1.
The XRD spectrum of the sub- silicon materials of the oxidation that this comparative example obtains is shown in Figure 10, it is seen that except (main peak is located at 28.5 to silicon in figure
Degree), silica (being located at 20 degree of amorphous packets) is free of any other object phase outside.
Figure 11,12 are the circulation for the negative electrode material that this comparative example obtains, multiplying power figure.Compared with comparative example, the present invention is obtained
Silicon based composite material have first effect high, stable circulation, the excellent feature of multiplying power.
Silicon based composite material obtained carries out chemical property comparing result and is shown in Table 1 in embodiment 1-8 and comparative example 1.
Table 1
As seen from Table 1, the present invention is regulated and controled by phase structure, obtains the silicon based composite material
Generally have first effect high compared to the sub- silicon of common oxidation in comparative example, recycles, the excellent feature of high rate performance.In addition, passing through
The ratio for adjusting compound phase can further adjust material emphasis in head effect and cycle performance.
In addition, inventor has carried out many experiments within the scope of the invention, by the type for changing the element in material
With content etc., preparing general formula of the invention respectively is SiAxOy, wherein A be B, Al, Na, Mg, Ca, Ba, Ti, Mn, Fe, Co,
One of Ni, Cu, Zn, Zr, Mo, Ge, Sn or a variety of, wherein x is greater than 0.001 and less than 10, y greater than 0.1 and less than 10
Silicon based composite material.
In certain embodiments, in silicon based composite material of the invention, B element is closed in the material with boron oxide, borosilicate
Gold exists with other elements compounding modes, and the highest peak of the corresponding XRD diffraction maximum of the boron oxide is located at 27.8 degree, institute
The highest peak for stating the corresponding XRD diffraction maximum of borosilicate alloy is located at 33.4 degree.
In certain embodiments, in silicon based composite material of the invention, Al element is in the material with aluminium oxide, alumina silicate
Or exist with other elements compounding modes, the highest peak of the corresponding XRD diffraction maximum of the aluminium oxide is located at 42.7 degree, described
The highest peak of the corresponding XRD diffraction maximum of alumina silicate is located at 26.6 degree and/or 26.2 degree.
In certain embodiments, in silicon based composite material of the invention, Na element in the material with sodium metasilicate or with
Other elements compounding modes exist, and the sodium metasilicate is Na2(Si3O7)、Na2(Si2O5) and Na (SiO3) one of or it is a variety of
Mixing.
In certain embodiments, in silicon based composite material of the invention, Mg element is in the material with magnesia, magnesium silicate
Or exist with other elements compounding modes, the highest peak of the corresponding XRD diffraction maximum of the magnesia is located at 42.9 degree, described
Magnesium silicate is MgSiO3、Mg2SiO4And Mg2Si2O6One of or a variety of mixing, wherein Mg2SiO4Corresponding XRD is at 37.3 degree
With 38.4 degree at have a pair of of characteristic peak.
In certain embodiments, in silicon based composite material of the invention, Ca element is in the material with calcium oxide, calcium silicates
Or exist with other elements compounding modes, the highest peak of the corresponding XRD diffraction maximum of the calcium oxide is located at 37.4 degree, described
Calcium silicates is CaSiO3、CaSi2O5、Ca2SiO4And Ca3Si3O9One of or a variety of mixing.
In certain embodiments, in silicon based composite material of the invention, Ba element is in the material with barium monoxide, barium silicate
Or exist with other elements compounding modes, the highest peak of the corresponding XRD diffraction maximum of the barium monoxide is located at 28.1 degree, described
Barium silicate is BaSiO3、BaSi2O5、Ba2SiO4、Ba4Si6O16And Ba6Si10O26One of or a variety of mixing.
In certain embodiments, in silicon based composite material of the invention, Ti element is closed in the material with titanium oxide, titanium silicon
Gold exists with other elements compounding modes, and the titanium oxide is TiO2、Ti2O3And Ti3O5Deng one or more of mixtures,
The titanium silicon is TiSi2、Ti5Si4、Ti5Si3With the combination of one or more of TiSi, corresponds to XRD and exist respectively
40.4, there is characteristic peak at 37.2,40.8 and 36.9 degree.
In certain embodiments, in silicon based composite material of the invention, Mn element is closed in the material with manganese oxide, manganese silicon
Gold, manganous silicate exist with other elements compounding modes, and the manganese oxide is MnO2、Mn3O4And Mn2O3One or more of
Mixing, the manganese-silicon be Mn3Si, MnSi and Mn5Si2One or more of mixing, correspond to XRD exist respectively
44.8, there is characteristic peak at 44.4 and 43.1 degree, the manganous silicate is MnSiO3, corresponding to XRD has characteristic peak at 32.5 degree.
In certain embodiments, in silicon based composite material of the invention, Fe element is closed in the material with iron oxide, iron silicon
Gold, ferrosilite exist with other elements compounding modes, and the iron oxide is Fe2O3, corresponding to XRD has feature at 33.2 degree
Peak, the ferro-silicium are FeSi2And/or FeSi, corresponding XRD have characteristic peak, the silicic acid at 17.3,45.0 degree respectively
Iron is FeSiO3And/or Fe2SiO4。
In certain embodiments, in silicon based composite material of the invention, Co element is closed in the material with cobalt oxide, cobalt silicon
Gold, cobaltous silicate exist with other elements compounding modes, and the cobalt oxide is Co3O4And/or CoO, corresponding XRD exist respectively
36.8, there is characteristic peak at 42.4 degree, the cobalt silicon alloy is CoSi, Co2Si and CoSi2One or more of mixing, it is corresponding
XRD have characteristic peak at 45.7,45.3 and 47.9 degree respectively, the cobaltous silicate is CoSiO3And/or Co2SiO4。
In certain embodiments, in silicon based composite material of the invention, Ni element is closed in the material with nickel oxide, nisiloy
Gold, silicic acid nickel exist with other elements compounding modes, and the nickel oxide is NiO and/or NiO2, corresponding XRD exists respectively
43.3, there is characteristic peak at 18.6 degree, the nickel silicon alloy is NiSi, Ni2Si、Ni3Si2And Ni3One of Si is several
Mixing, corresponding XRD have characteristic peak at 47.2,46.2,45.0 and 44.7 degree respectively, and the silicic acid nickel is Ni2SiO4。
In certain embodiments, in silicon based composite material of the invention, Cu element is in the material with cupro silicon, silicic acid
Ketone exists with other elements compounding modes, and the cupro silicon is Cu9Si、Cu5Si、Cu6.6Si、Cu15Si4And Cu3In Si
One or several kinds of mixing, corresponding XRD has characteristic peak at 43.3,43.7,43.2,44.1,45.0 degree respectively, described
Silicic acid ketone is CuSiO3, corresponding XRD has characteristic peak at 28.0 degree.
In certain embodiments, in silicon based composite material of the invention, Zn element is in the material with zinc oxide, zinc silicate
Or exist with other elements compounding modes, the zinc oxide is ZnO and/or ZnO2, corresponding XRD is respectively 42.3,37.0
There is characteristic peak at degree；The zinc silicate is ZnSiO3And/or Zn2SiO4。
In certain embodiments, in silicon based composite material of the invention, Zr element is in the material with zirconium silicon alloy, silicic acid
Zirconium exists with other elements compounding modes, and the zirconium silicon alloy is Zr2Si、Zr5Si3、ZrSi2、Zr5Si4And Zr3Si2In one
Kind or several mixing, the zirconium silicate are ZrSiO4, XRD has characteristic peak at 27.0 degree.
In certain embodiments, in silicon based composite material of the invention, Mo element in the material with molybdenum-silicon alloy or
Exist with other elements compounding modes, the molybdenum-silicon alloy is MoSi2、Mo5Si3And Mo3One of Si or mixing.
In certain embodiments, in silicon based composite material of the invention, Ge element is in the material with arbitrary proportion
GeSi alloy, germanium oxide exist with other elements compounding modes, and the germanium oxide is GeO2, XRD has at 26.4 degree
Characteristic peak.
In certain embodiments, in silicon based composite material of the invention, Sn element is in the material with tin oxide, metal
Tin or exist with other elements compounding modes, the tin oxide is SnO2And/or SnO, corresponding XRD respectively 26.5 degree,
There is characteristic peak at 29.9 degree；The metallic tin is simple substance Sn, and corresponding XRD has characteristic peak at 30.6 degree.
Silicon based composite material of the invention generally has first effect high, recycles, the excellent feature of high rate performance.
Claims (11)
1. a kind of silicon based composite material, general formula SiAxOy, wherein A be B, Al, Na, Mg, Ca, Ba, Ti, Mn, Fe, Co, Ni,
One of Cu, Zn, Zr, Mo, Ge, Sn or a variety of, wherein x is greater than 0.001 and less than 10, y greater than 0.1 and less than 10.
2. silicon based composite material as described in claim 1, wherein the microstructure of the silicon based composite material is multiphase disperse
Distribution, the silicon based composite material include at least a kind of metal phase, a kind of metal oxide phase and/or composite oxides phase；
Preferably, wherein the content of the metal phase is the 20%-90% of the silicon based composite material gross mass, more preferably
30%-60%；The content of the metal oxide phase and/or composite oxides phase is the silicon based composite material gross mass
20%-90%, more preferably 30%-60%.
3. silicon based composite material as claimed in claim 2, wherein the size of the metal phase is 0.5-100nm；Preferably, institute
Metal phase is stated by one of Si and B, Al, Na, Mg, Ca, Ba, Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ge, Sn or a variety of
Simple substance or composition of alloy.
4. silicon based composite material as claimed in claim 2 or claim 3, wherein the metal phase is evenly distributed on one or more metals
In oxide phase and/or composite oxides phase；Preferably, the metal oxide be mutually Si, B, Al, Na, Mg, Ca, Ba, Ti,
One of Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ge, Sn or a variety of oxides, the composite oxides be mutually Si, B,
One of Al, Na, Mg, Ca, Ba, Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ge, Sn or a variety of composite oxides.
5. silicon based composite material as described in claim 1, wherein the B element in the material with boron oxide, borosilicate alloy or
Person exists with other elements compounding modes, and the highest peak of the corresponding XRD diffraction maximum of the boron oxide is located at 27.8 degree, the boron
The highest peak of the corresponding XRD diffraction maximum of silicon alloy is located at 33.4 degree；
The Al element in the material by aluminium oxide, alumina silicate or with other elements compoundings in a manner of exist, the aluminium oxide
The highest peak of corresponding XRD diffraction maximum is located at 42.7 degree, and the highest peak of the corresponding XRD diffraction maximum of the alumina silicate is located at 26.6
Degree and/or 26.2 degree at；
The Na element in the material by sodium metasilicate or with other elements compoundings in a manner of exist, the sodium metasilicate is Na2
(Si3O7)、Na2(Si2O5) and Na (SiO3) one of or a variety of mixing；
The Mg element in the material by magnesia, magnesium silicate or with other elements compoundings in a manner of exist, the magnesia
The highest peak of corresponding XRD diffraction maximum is located at 42.9 degree, and the magnesium silicate is MgSiO3、Mg2SiO4And Mg2Si2O6In one
Kind or a variety of mixing, wherein Mg2SiO4Corresponding XRD has a pair of of characteristic peak at 37.3 degree and 38.4 degree；
The Ca element in the material by calcium oxide, calcium silicates or with other elements compoundings in a manner of exist, the calcium oxide
The highest peak of corresponding XRD diffraction maximum is located at 37.4 degree, and the calcium silicates is CaSiO3、CaSi2O5、Ca2SiO4And Ca3Si3O9
One of or a variety of mixing；
The Ba element in the material by barium monoxide, barium silicate or with other elements compoundings in a manner of exist, the barium monoxide
The highest peak of corresponding XRD diffraction maximum is located at 28.1 degree, and the barium silicate is BaSiO3、BaSi2O5、Ba2SiO4、Ba4Si6O16
And Ba6Si10O26One of or a variety of mixing；
The Ti element in the material by titanium oxide, titanium silicon or with other elements compoundings in a manner of exist, the oxidation
Titanium is TiO2、Ti2O3And Ti3O5Deng one or more of mixtures, the titanium silicon is TiSi2、Ti5Si4、Ti5Si3With
The combination of one or more of TiSi, corresponding to XRD has characteristic peak at 40.4,37.2,40.8 and 36.9 degree respectively；
The Mn element in the material by manganese oxide, manganese-silicon, manganous silicate or with other elements compoundings in a manner of exist, institute
Stating manganese oxide is MnO2、Mn3O4And Mn2O3One or more of mixing, the manganese-silicon be Mn3Si, MnSi and Mn5Si2
One or more of mixing, correspond to XRD have characteristic peak at 44.8,44.4 and 43.1 degree respectively, the manganous silicate is
MnSiO3, corresponding to XRD has characteristic peak at 32.5 degree；
The Fe element in the material by iron oxide, ferro-silicium, ferrosilite or with other elements compoundings in a manner of exist, institute
Stating iron oxide is Fe2O3, correspond to XRD has characteristic peak at 33.2 degree, and the ferro-silicium is FeSi2And/or FeSi, it is corresponding
XRD has characteristic peak at 17.3,45.0 degree respectively, and the ferrosilite is FeSiO3And/or Fe2SiO4；
The Co element in the material by cobalt oxide, cobalt silicon alloy, cobaltous silicate or with other elements compoundings in a manner of exist, it is described
Cobalt oxide is Co3O4And/or CoO, corresponding XRD have a characteristic peak at 36.8,42.4 degree respectively, the cobalt silicon alloy be CoSi,
Co2Si and CoSi2One or more of mixing, corresponding XRD has characteristic peak at 45.7,45.3 and 47.9 degree respectively, institute
Stating cobaltous silicate is CoSiO3And/or Co2SiO4；
The Ni element in the material by nickel oxide, nickel silicon alloy, silicic acid nickel or with other elements compoundings in a manner of exist, institute
Stating nickel oxide is NiO and/or NiO2, corresponding XRD has characteristic peak at 43.3,18.6 degree respectively, and the nickel silicon alloy is
NiSi、Ni2Si、Ni3Si2And Ni3One of Si or several mixing, corresponding XRD is respectively in 47.2,46.2,45.0 and
There is characteristic peak at 44.7 degree, the silicic acid nickel is Ni2SiO4；
The Cu element in the material by cupro silicon, silicic acid ketone or with other elements compoundings in a manner of exist, the copper silicon
Alloy is Cu9Si、Cu5Si、Cu6.6Si、Cu15Si4And Cu3One of Si or several mixing, corresponding XRD exist respectively
There is characteristic peak at 43.3,43.7,43.2,44.1,45.0 degree, the silicic acid ketone is CuSiO3, corresponding XRD has at 28.0 degree
Characteristic peak；
The Zn element in the material by zinc oxide, zinc silicate or with other elements compoundings in a manner of exist, the zinc oxide
For ZnO and/or ZnO2, corresponding XRD has characteristic peak at 42.3,37.0 degree respectively；The zinc silicate is ZnSiO3And/or
Zn2SiO4；
The Zr element in the material by zirconium silicon alloy, zirconium silicate or with other elements compoundings in a manner of exist, the zirconium silicon
Alloy is Zr2Si、Zr5Si3、ZrSi2、Zr5Si4And Zr3Si2The mixing of middle one or more, the zirconium silicate are ZrSiO4,
XRD has characteristic peak at 27.0 degree；
The Mo element in the material by molybdenum-silicon alloy or with other elements compoundings in a manner of exist, the molybdenum-silicon alloy is
MoSi2、Mo5Si3And Mo3One of Si or mixing；
The Ge element in the material by the GeSi alloy of arbitrary proportion, germanium oxide or with other elements compoundings in a manner of deposit
It is GeO in, the germanium oxide2, XRD has characteristic peak at 26.4 degree；And/or
The Sn element in the material by tin oxide, metallic tin or with other elements compoundings in a manner of exist, the tin oxide
For SnO2And/or SnO, corresponding XRD have characteristic peak at 26.5 degree, 29.9 degree respectively；The metallic tin is simple substance Sn, corresponding
XRD has characteristic peak at 30.6 degree；
Wherein, the XRD diffraction maximum is characteristic peak being obtained using Cu-K α actinometry, being indicated with 2 θ angles, precision
It is ± 0.2 degree.
6. the silicon based composite material as described in any one of claims 1 to 5, wherein the average grain diameter of the silicon based composite material
It is 50 nanometers~40 microns；Preferably, the average grain diameter of the silicon based composite material is 1 micron~10 microns；It is highly preferred that institute
It is 400-2500mAh/g that silicon based composite material, which is stated, as the charge specific capacity of negative electrode material.
7. a kind of method for preparing silicon based composite material as claimed in any one of claims 1 to 6, be a step vapour deposition process or
Two-step method, in which:
The one step vapour deposition process is the following steps are included: by one or both of elemental silicon, the oxide of simple substance A and A, Yi Jiren
The silica of choosing is added as after the ratio mixing of elemental mole ratios Si:A:O=1:x:y through beam bombardment, magnetron sputtering, electric induction
Heat, resistance heating to the modes such as 800-1800 DEG C, which are evaporated to, to be deposited on the substrate that temperature is 50-800 DEG C after gas, later will
Deposit is broken for powder, obtains the silicon based composite material；
The two-step method the following steps are included: through beam bombardment, magnetic control after first mixing elemental silicon and silica in proportion
The modes such as sputtering, electrical induction, resistance heating are deposited as aoxidizing sub- silicon after being evaporated to gas, later with simple substance A and/or A
Oxide carries out heat treatment 2-24h at 600-1500 DEG C after evenly mixing, obtains the silicon based composite material.
8. the method for claim 7, which is characterized in that the simple substance A be B, Al, Na, Mg, Ca, Ba, Ti, Mn, Fe,
Any one in Co, Ni, Cu, Zn, Zr, Mo, Ge, Sn or a variety of simple substance element or intermetallic compound.
9. a kind of negative electrode material, it includes silicon based composite material described in any one of claims 1 to 6 and carbon materials, wherein
The content of the silicon based composite material is 2% or more of the negative electrode material gross mass；The carbon material include soft carbon, hard carbon,
One or more of carbonaceous mesophase spherules, graphitized intermediate-phase carbosphere, natural graphite, modified natural graphite and artificial graphite
Combination；Preferably, carbon coating processing is carried out to the silicon based composite material.
10. a kind of battery or lithium-ion capacitor, it includes silicon based composite materials such as described in any one of claims 1 to 6
Or negative electrode material as claimed in claim 9；Preferably, the battery is lithium ion battery, lithium-sulfur cell or all-solid-state battery.
11. the purposes of negative electrode material as claimed in claim 9 is used for as lithium ion battery, lithium-ion capacitor, lithium sulphur electricity
The negative electrode material or part of it of pond or all-solid-state battery.
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