CN106328909A - Nano-silica-silicone-based composite material, preparation method and lithium ion battery comprising composite material - Google Patents
Nano-silica-silicone-based composite material, preparation method and lithium ion battery comprising composite material Download PDFInfo
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- CN106328909A CN106328909A CN201611031476.7A CN201611031476A CN106328909A CN 106328909 A CN106328909 A CN 106328909A CN 201611031476 A CN201611031476 A CN 201611031476A CN 106328909 A CN106328909 A CN 106328909A
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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
- H01M4/364—Composites as mixtures
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 invention relates to a nano-silica-silicone-based composite material, a preparation method thereof and a lithium ion battery comprising the composite material. The nano-silica-silicone-based composite material comprises a carbon substrate and composite particles evenly scattered in the carbon substrate. The composite particles comprise nano-silica-silicone particles of core-shell structures and conducting carbon layers arranged on the surfaces of the particles in a coating mode. The method comprises the steps that the nano-silica-silicone particles of the core-shell structures are prepared by controlling parameters such as the use quantity of a reducing agent and an additive, then the surfaces of the particles are coated in-situ with the conducting carbon layers through the homogeneous phase coating technology, then the composite particles obtained through carbon coating are scattered in the carbon substrate through the fusion technology, and the nano-silica-silicone-based composite material is obtained. The battery made of the composite material being a negative electrode material has the advantages of high specific capacity (larger than 930.5 mAh/g), long cycle life (the capacity retention rate of 100 cycles is 93.8% or above) and high conductivity.
Description
Technical field
The invention belongs to electrochemical field and lithium ion battery negative material application, relate to a kind of composite, system
Preparation Method and comprise the lithium ion battery of this composite, particularly relates to a kind of nano silicon-silicon based composite material, its system
Preparation Method, and comprise this composite lithium ion battery as negative material.
Background technology
Lithium ion battery is energy accumulating device the most of greatest concern, is mainly used in 3C field, recently as newly
Energy automobile market development, it the most constantly extends in power vehicle application.Along with market is fast-developing, close to the energy content of battery
Degree requires more and more higher.And the performance of electrode material is the key point determining lithium ion battery energy density in battery.When
Front business-like lithium battery typically uses carbon material as negative pole, and cobalt acid lithium is as positive pole.But the theoretical specific energy of material with carbon element is only
There is 372mAh g-1, far from reaching follow-on lithium ion battery demand.
In various Novel anode materials, silicon materials are with its high-energy-density, low-voltage platform and abundance
It is generally considered one of candidate material of future generation etc. advantage.But there is a fatal defect as negative material in silicon: follows
Volumetric expansion change huge during ring, produces stress and easily causes material generation efflorescence to crush, ultimately cause cycle performance
Slump of disastrous proportions.
For solving silicon volumetric expansion problem, targetedly, market develops silicon-carbon and two kinds of technology paths of silica.Its
Middle silica have employed and utilizes silicon to be scattered in this characteristic in silica network structure effectively to suppress silicon volumetric expansion.Oxygen is in silicon
On the one hand impact mainly includes two aspects that, oxygen introducing can cause the efficiency first of material and specific capacity to decline, simultaneously because silicon oxidation
The electric conductivity of thing is lower, and the performance of material own can more deteriorate；On the other hand, can be more than Si prediction due to silica bond energy
By force, the Si oxide of formation is more stable, and Lithium-ion embeding can form irreversible Li2O and Li2SiO4, serve as a cushion
Left and right, can effectively alleviate volumetric expansion, the cyclical stability of reinforcing material.Introduce the silicon materials of appropriate oxygen, sacrifice certain effect
Rate and specific capacity, it is thus achieved that more useful cycle performance, this is also a trend of current silica-base material development, but specifically draws
Entering the oxygen of which kind of form, the oxygen-containing silicon based composite material preparing which kind of structure just can make battery have more preferable cycle performance still
It it is a difficult problem.
Summary of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of nano silicon-silicon
Based composites, its preparation method and comprise the lithium ion battery of this composite.The nano silicon of the present invention-silica-based multiple
Condensation material Stability Analysis of Structures, is applied to lithium ion battery as negative material and shows the cycle performance of excellence, reversible capacity first
At more than 930.5mAh/g, coulombic efficiency is more than 83.2% first, and 100 circulation volume conservation rates are more than 93.8%.
First aspect, the present invention provides a kind of nano silicon-silicon based composite material, and described composite includes carbon back
Matter and the composite particles being dispersed in carbon matrix, described composite particles includes the nano silicon-silicon of nucleocapsid structure
Granule and be coated on the conductive carbon layer on nano silicon-silicon grain surface.
Preferably, the median particle diameter of described nano silicon-silicon based composite material is 1～45 μm, such as 2 μm, 4 μm,
10 μm, 11 μm, 14 μm, 17 μm, 22 μm, 24 μm, 32 μm, 36 μm, 40 μm, 43 μm or 45 μm etc., preferably 3～35 μm, enter one
Step is preferably 5～25 μm, particularly preferably 5～15 μm.
Preferably, the specific surface area of described nano silicon-silicon based composite material is 1～55m2/ g, such as 3m2/g、
5m2/g、10m2/g、15m2/g、16m2/g、19m2/g、24m2/g、28m2/g、32m2/g、36m2/g、40m2/g、45m2/g、50m2/
g、52m2/ g or 55m2/ g etc., preferably 2～20m2/ g, more preferably 3～15m2/g。
Preferably, the powder body compacted density of described nano silicon-silicon based composite material is 0.4～2.6g/cm3, example
Such as 0.4g/cm3、0.8g/cm3、1.2/cm3、1.5g/cm3、2g/cm3Or 2.6g/cm3Deng, preferably 0.5～2.2g/cm3, enter
One step is preferably 0.9～2g/cm3, preferably 0.7～1.8g/cm3。
Preferably, it is in terms of 100% by the gross mass of composite, in described composite, the quality hundred of described carbon matrix
Proportion by subtraction is 10～60wt%, such as 10wt%, 15wt%, 21wt%, 25wt%, 30wt%, 32wt%, 35wt%, 40wt%,
44wt%, 47wt%, 52wt% or 58wt% etc., preferably 20～60wt%.
Preferably, it is in terms of 100% by the gross mass of composite, in described composite, described nano silicon-silicon
The mass percent of core-shell structure particles is 5～80wt%, such as 5wt%, 14wt%, 17wt%, 22wt%, 27wt%,
29wt%, 31wt%, 44wt%, 49wt%, 53wt%, 60wt%, 71wt% or 80wt% etc..
Preferably, it is in terms of 100% by the gross mass of described composite, in described composite, described conductive carbon layer
Mass percent is 1～40wt%, such as 1wt%, 4wt%, 11wt%, 15wt%, 21wt%, 25wt%, 32wt%,
35wt%, 38wt% or 40wt% etc..
Preferably, the structure of described nano silicon-silicon grain is nucleocapsid structure, described nano silicon-silicon
The kernel of grain is nanometer silicon dioxide particle, and shell is nanometer silicon layer.
Preferably, the particle diameter of kernel nanometer silicon dioxide particle is 1～50nm, such as 2nm, 4nm, 8nm, 13nm, 15nm,
20nm, 25nm, 30nm, 34nm, 40nm, 45nm, 48nm or 50nm etc..
Preferably, the thickness of shell nanometer silicon layer is 5～40nm, such as 5nm, 10nm, 15nm, 20nm, 24nm, 28nm,
32nm, 35nm, 38nm or 40nm etc..
Preferably, the oxygen content of nano silicon-silicon grain is 8%～40wt%, such as 8wt%, 12wt%,
15wt%, 22wt%, 28wt%, 33wt%, 36wt% or 40wt% etc..
Preferably, the specific surface area of nano silicon-silicon grain is 20～500m2/ g, such as 20m2/g、35m2/g、
50m2/g、70m2/g、80m2/g、120m2/g、140m2/g、160m2/g、200m2/g、240m2/g、260m2/g、285m2/g、
300m2/g、330m2/g、360m2/g、400m2/g、450m2/ g or 500m2/ g etc., preferably 50～400m2/g。
Second aspect, the present invention provides the preparation side of nano silicon-silicon based composite material as described in relation to the first aspect
Method, said method comprising the steps of:
(1) by nano-silicon oxide, reducing agent and additive according to 1:(0.5～1): (1～12) mix, and carry out homogeneously multiple
Close, subsequently heat-treated, then heat-treated products is washed and acid treatment, obtain the nano silicon-silicon of nucleocapsid structure
Grain；
(2) nano silicon-silicon grain in step (1) is carried out homogeneous in-situ carbon cladding, obtain by nano-silica
The composite particles that SiClx-silicon grain and conductive carbon layer are constituted, wherein, conductive carbon layer is coated on nano silicon-silicon grain
Surface；
(3) composite particles that step (2) obtains homogeneously is combined with carbon source, fusion treatment, then heat treatment, obtains nanometer two
Silicon oxide-silicon based composite material.
Preferably, the mass ratio of step (1) described nano-silicon oxide, reducing agent and additive is 1:(0.5～1): (1
～12), such as 1:0.5:1,1:0.6:4,1:0.7:12,1:0.8:8,1:0.9:10,1:0.3:11,1:0.5:8,1:0.6:
12,1:0.2:9 or 1:0.3:10 etc..
In step of the present invention (1), the melted heat absorption of additive, it is anti-that the addition of appropriate additive can be good at absorbing reduction
Answer liberated heat, control reaction temperature, on the one hand can avoid the generation of the impurity such as metal silicide, improve reaction and convert
Rate；On the other hand can also suppress growing up of nano-silicon, coordinate the use of appropriate reducing agent, advantageously form the core of low crystal grain value
Nano silicon-the silicon grain of shell structure, in the present invention, the addition of additive is requisite step.
In step of the present invention (1), by controlling addition and the addition of additive of reducing agent, nucleocapsid can be controlled
Kernel nano silicon and the ratio of shell nanometer silicon layer in structure, form the nano silicon-silicon of nucleocapsid structure
Grain, is conducive to promoting the cycle life of material.
In order to preferably play the effect that heat is regulated and controled by additive, to be more beneficial for preparing the nano-silica of nucleocapsid structure
SiClx-silicon grain, the mass ratio of preferred nano-silicon oxide and additive is 1:(8～12).
In order to reach more preferable reduction effect to prepare the nano silicon-silicon grain of nucleocapsid structure, both will not make to receive
Rice Si oxide is reduced into nano-silicon completely, is not result in that again reducing degree is inadequate, preferred nano-silicon oxide and reduction
The mass ratio of agent is 1:(0.5～0.8), nano silicon-silicon grain that reaction obtains is nucleocapsid structure, described nano-silica
The kernel of SiClx-silicon grain and shell are respectively nanometer silicon dioxide particle and nanometer silicon layer.
As the optimal technical scheme of the preparation method of silicon based composite material of the present invention, described method is additionally included in
After step (3) heat treatment completes, heat-treated products is pulverized, sieves and is removed the step of magnetic.
Preferably, the chemical composition of step (1) described nano-silicon oxide is SiOx, wherein, 1≤X≤2, such as X are 1,
1.2,1.5,1.8 or 2 etc..
Preferably, the median particle diameter of step (1) described nano-silicon oxide is 1～160nm, such as 1nm, 5nm, 10nm,
20nm, 30nm, 40nm, 45nm, 50nm, 60nm, 70nm, 85nm, 100nm, 115nm, 125nm, 140nm, 150nm or 160nm
Deng.
Preferably, in step (1), reducing agent includes appointing in the metal simple-substances such as potassium, calcium, sodium, magnesium, aluminum, zinc, ferrum, copper and mickel
Anticipating a kind of or combination of at least two, but be not limited to the above-mentioned metal enumerated, other can play the reducing agent of phase same-action also
Can be used for the present invention.
Preferably, the median particle diameter of step (1) described reducing agent is 20～50 μm, such as 20 μm, 25 μm, 30 μm, 35 μm,
40 μm, 42 μm, 45 μm, 46 μm, 48 μm or 50 μm etc..
Preferably, the mass ratio of step (1) described nano-silicon oxide and described reducing agent is 1:(0.5～0.8), such as
1:0.5,1:0.6,1:0.65,1:0.7,1:0.75 or 1:0.8 etc..
Preferably, step (1) described additive includes potassium chloride, potassium carbonate, potassium nitrate, potassium sulfate, sodium chloride, carbonic acid
Any one or the combination of at least two in sodium, sodium nitrate or sodium sulfate.
Additive in the present invention is not limited to the above-mentioned additive enumerated, it is also possible to be that other can reach phase same-action
Additive, but must be fulfilled for following 2 requirements: 1. the fusing point of additive is at 600～900 DEG C, and close with reaction temperature (add
Add the fusing point of agent with the difference of reaction temperature at 50～100 DEG C)；2. additive not with reactant (nano-silicon oxide and reduction
Agent) react.
Preferably, the median particle diameter of step (1) described additive is 100～200 mesh, such as 100 mesh, 120 mesh, 150 mesh
Or 200 mesh etc..
Preferably, step (1) is described is homogeneously complex as: nano-silicon oxide, additive and reducing agent are homogeneously mixed
Close, obtain homogeneous mixture.
Preferably, the method that described homogeneous mixing uses includes dry mixing methods and wet-mixed method, is preferably dry
Method mixed method.
Preferably, described dry mixing methods is dry ball milling method or is placed in the method carrying out in VC mixer mixing.
Preferably, in described dry ball milling method use ball mill be planetary ball mill, high-speed stirred mill, tube mill,
Any one in type taper grinder, rod mill and sand mill.
Preferably, being placed in VC mixer the method carrying out mixing described in is: by the nano-silicon oxide of step (1), go back
Former dose is placed in VC mixer with additive, mixes, obtain homogeneous mixture.
Preferably, step (1) described heat treatment is: be placed in hermetic container by homogeneous mixture, at non-oxidizing atmosphere
Under carry out heat treatment.
Preferably, in step (1) described heat treatment process, described non-oxidizing atmosphere is nitrogen atmosphere, hydrogen atmosphere, helium
Any one or the combination of at least two in gas atmosphere, argon gas atmosphere or neon atmosphere.
Preferably, the temperature of step (1) described heat treatment is 600～950 DEG C, such as 600 DEG C, 620 DEG C, 630 DEG C, 640
DEG C, 660 DEG C, 680 DEG C, 710 DEG C, 750 DEG C, 780 DEG C, 805 DEG C, 825 DEG C, 850 DEG C, 880 DEG C, 910 DEG C or 950 DEG C etc..
Preferably, the time of step (1) described heat treatment is 1～6h, such as 1h, 1.3h, 1.5h, 2h, 2.5h, 3h,
3.5h, 4h, 4.2h, 4.4h, 4.6h, 5h, 5.5h or 6h etc..
Preferably, step (1) described acid treatment is: be placed in container by heat-treated products, adds acid, processes.
Preferably, during step (1) described acid treatment, described in be processed as soak, or soak and with stirring.
Preferably, during step (1) described acid treatment, the time of described process is 1～8h, such as 1h, 2h, 3h, 4h,
4.5h, 5h, 6h, 7h or 8h etc., preferably 1～4h.
Preferably, during step (1) described acid treatment, described acid selected from can with reducing agent metal (M=K, Ca, Na,
Mg, Al, Zn, Fe, Cu or Ni) oxide (K that formed2O、CaO、Na2O、MgO、Al2O3、ZnO、Fe2O3, CuO and NiO etc.) anti-
The more active acid answered, preferably hydrochloric acid, nitric acid, nitrous acid, sulphuric acid, sulfurous acid, carbonic acid, boric acid, phosphoric acid, hydrocyanic acid, high chlorine
Any one or the combination of at least two in acid, acetic acid, benzoic acid or selenic acid.Avoid during acid treatment of the present invention using poison
The Fluohydric acid. that property is strong, preparation process environmental protection.
Preferably, during step (1) described acid treatment, the concentration of described acid is 0.1～10mol/L, such as
0.1mol/L、0.5mol/L、1mol/L、2mol/L、3mol/L、3.5mol/L、4mol/L、4.5mol/L、5mol/L、6mol/
L, 7mol/L, 8mol/L, 9mol/L or 10mol/L etc..
Preferably, described method be additionally included in after step (1) acid treatment completes be centrifuged, sucking filtration and dry step.
Preferably, the method that step (2) described homogeneous in-situ carbon cladding uses is gas phase cladding, liquid phase coating method or solid
Any one in phase cladding process, preferably gas phase cladding.
Preferably, using gas phase cladding to carry out homogeneous in-situ carbon cladding, described gas phase cladding is: to equipped with nanometer two
In the reacting furnace of silicon oxide-silicon grain, it is passed through gas phase carbon source, under conditions of reacting furnace rotates, carries out in-situ deposition cladding,
To the composite particles being made up of nano silicon-silicon grain and conductive carbon layer, wherein, conductive carbon layer is coated on described nanometer two
The surface of silicon oxide-silicon grain.
Preferably, in described gas phase cladding, described gas phase carbon source be methane, ethane, propane, ethylene, acetylene, propylene,
Any one or at least two in the acetone of the benzene of gaseous state, the toluene of gaseous state, the dimethylbenzene of gaseous state, the ethanol of gaseous state or gaseous state
Combination, the preferably combination of the toluene of methane, acetylene and gaseous state.
Preferably, in described gas phase cladding, the rotary speed of described reacting furnace is 0.2～8rpm, such as 0.2rpm,
0.8rpm, 1rpm, 1.3rpm, 1.8rpm, 2.2rpm, 3rpm, 4rpm, 5rpm, 6rpm, 7rpm or 8rpm etc..
Preferably, in described gas phase cladding, the flow that is passed through of described gas phase carbon source is 0.1～1.2L/min, such as
0.1L/min, 0.5L/min, 0.8L/min, 1L/min or 1.2L/min etc..
Preferably, in described gas phase cladding, the temperature of described in-situ deposition cladding is 600～1000 DEG C, such as 600
DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C or 1000 DEG C etc., preferably 800～1000 DEG C.
Preferably, in described gas phase cladding, described in-situ deposition cladding time be 3～6h, such as 3h, 3.5h, 4h,
4.2h, 4.5h, 5h, 5.2h, 5.4h, 5.6h or 6h etc..
In the present invention, by vapour deposition, the nano silicon-silicon grain of nucleocapsid structure is carried out homogeneous in-situ carbon bag
Cover, improve the electrical conductivity of granule, be conducive to promoting the high rate performance of material；Additionally nano grain surface carbon coating layer can suppress
The side reaction of active substance nano silicon-between silicon grain and electrolyte, is conducive to improving the stability of material.
Preferably, the method for the described homogeneous Combined Mining of step (3) is solid phase cladding process, liquid phase coating method or gas phase cladding
Any one in method, preferably solid phase cladding process.
Preferably, step (3) described fusion treatment includes: composite particles step (2) obtained and carbon source mix homogeneously
Rear addition, in fusion machine, is merged.
Preferably, during described fusion treatment, the rotating speed merging machine is 600～3000rpm, such as 600rpm,
800rpm, 1000rpm, 1300rpm, 1500rpm, 1700rpm, 2000rpm, 2400rpm, 2700rpm or 3000rpm etc., excellent
Elect 300～2000rpm as.
Preferably, during described fusion treatment, the cutter gap merging machine is 0.01～1cm, such as 0.05cm,
0.1cm, 0.2cm, 0.3cm, 0.4cm, 0.5cm, 0.6cm, 0.7cm, 0.8cm or 1cm etc., preferably 0.1～0.3cm.
Preferably, during described fusion treatment, the time of fusion is at least 0.25h, such as 0.25h, 1h, 2.5h,
4h, 6h, 8h, 15h, 16h, 24h, 28h, 36h, 40h, 48h or 52h etc., preferably 0.25～8h, particularly preferably 0.5～4h.
Preferably, step (3) described carbon source is selected from coal tar pitch and petroleum asphalt, mesophase pitch, coal tar, petroleum industry weight
Matter oil, Heavy aromatic hydrocarbon, epoxy resin, phenolic resin, furfural resin, Lauxite, polyvinyl alcohol, polrvinyl chloride, poly-second two
Any one or the combination of at least two in alcohol, poly(ethylene oxide), Kynoar, acrylic resin or polyacrylonitrile.
Preferably, the particle diameter of step (3) described carbon source is 2～5 μm, such as 2 μm, 2.5 μm, 3 μm, 3.2 μm, 3.6 μm, 4 μ
M, 4.3 μm, 4.5 μm or 5 μm etc..
Preferably, step (3) described heat treatment process is connected with protection gas, and described protection gas is nitrogen, helium, neon, argon
Any one or the combination of at least two in gas or Krypton.
Preferably, the temperature of step (3) described heat treatment is 700～1000 DEG C, such as 700 DEG C, 720 DEG C, 750 DEG C, 775
DEG C, 800 DEG C, 820 DEG C, 850 DEG C, 900 DEG C, 950 DEG C or 1000 DEG C etc.
Preferably, the time of step (3) described heat treatment is 2～6h, such as 2h, 2.5h, 3h, 4h, 4.3h, 4.6h, 5h,
5.5h or 6h etc..
In the present invention, introduced by step (3) and merge and solid phase, gas phase and Liquid Coating Technology, granule outer layer is entered
Row uniformly cladding, defines the clad of densification at outer layer.
The third aspect, the present invention provides a kind of negative material, and described negative material is the nano-silica described in first aspect
SiClx-silicon based composite material.
Fourth aspect, the present invention provides a kind of lithium ion battery, and described lithium ion battery comprises receiving described in first aspect
Rice silicon dioxide-silicon based composite material is as the negative material in lithium ion battery.
Compared with prior art, there is advantages that
(1) present invention uses metal reduction Si oxide, by controlling the reduction reactions such as the consumption of reducing agent and additive
Parameter regulates and controls reducing degree, reaction temperature and silicon nanoparticle size, and suppresses impurity to generate, and has prepared nucleocapsid structure
Nano silicon-silicon grain, then by homogeneous coating technology nano silicon-silicon grain surface in situ be coated with
Conductive carbon layer and obtain composite particles, then by integration technology composite particles is dispersed in carbon matrix and obtains nano-silica
SiClx-silicon based composite material.The processing characteristics of the method for the invention is good, technique simple, and environmental friendliness is pollution-free, has very
Big application potential.
(2) nano silicon-silicon based composite material of the present invention includes carbon matrix and answering of being dispersed in carbon matrix
Closing granule, described composite particles is by low crystal grain value, the nano silicon-silicon grain of nucleocapsid structure and is coated on leading of its surface
Electrical carbon layer is constituted, and nucleocapsid structure, multilamellar carbon-coating mating reaction reduce material volumetric expansion in charge and discharge process jointly.Should
In the nano silicon-silicon grain of nucleocapsid structure, the expansion rate of nano-silicon own is relatively low, and nano silicon is in process of intercalation
The irreversible Li formed2O, Li2SiO4Deng, suppress volumetric expansion, and the granule oxygen ratio of this nucleocapsid structure be controlled,
There is lower expansion rate, be conducive to improving the cycle performance of material；The cladding of conductive carbon layer and the parcel of carbon matrix are the most favourable
In the electric conductivity of lifting material, improve electron mobility and high rate performance, moreover it is possible to reduce active substance nano silicon-silicon
Grain and the side reaction of electrolyte, improve stability of material.
(3), in the composite of the present invention, jointly act on the volumetric expansion reducing silicon in conjunction with oxygen and two kinds of elements of carbon, improve
The cycle performance of material and high rate performance.Using the composite of the present invention as the negative material of battery, prepared battery
Specific capacity is high, and coulombic efficiency is high first, and good cycle, reversible capacity is at more than 930.5mAh/g first, first coulombic efficiency
More than 83.2%, 100 circulation volume conservation rates are more than 93.8%.
Accompanying drawing explanation
Fig. 1 a is the organigram of the nano silicon-silica-based composite negative pole material of the present invention, and wherein, 1 represents carbon
Substrate；2 represent composite particles；
Fig. 1 b is the organigram of the composite particles in Fig. 1 a, and wherein, 3 represent nanometer silicon dioxide particle, and 4 representatives are received
Rice silicon layer, 5 represent conductive carbon layer；
The scanning of the nano silicon-silicon grain of the nucleocapsid structure that Fig. 2 is the embodiment of the present invention 1 to be prepared through step (1)
Ultramicroscope (SEM) picture；
Fig. 3 is the SEM figure of the nano silicon-silica-based composite negative pole material of the embodiment of the present invention 1 preparation；
Fig. 4 is the XRD figure spectrum of the nano silicon-silica-based composite negative pole material of the embodiment of the present invention 1 preparation；
Fig. 5 is that the nano silicon-silica-based composite negative pole material of the embodiment of the present invention 1 preparation is made battery and carries out electricity
Chemical property is tested, the first charge-discharge curve obtained；
Fig. 6 is that the nano silicon-silica-based composite negative pole material of the embodiment of the present invention 1 preparation is made battery and carries out electricity
Chemical property is tested, the cycle performance curve obtained.
Detailed description of the invention
Further illustrate technical scheme below in conjunction with the accompanying drawings and by detailed description of the invention.
Prepare at identical conditions using the composite that embodiment 1-5 and comparative example 1 prepare as negative material
Battery also tests the chemical properties such as its cycle performance, and the preparation method of concrete battery is as follows: by negative material, conductive agent carbon
Black SP and binding agent sodium carboxymethyl cellulose CMC mixes during 94:1:5 is dissolved in solvent deionized water by mass percentage, controls
Solid content, 50%, is coated in copper foil current collector, vacuum drying, prepare cathode pole piece, to electrode use metal lithium sheet,
The LiPF of 1.2mol/L6/ EC+DMC+EMC (v/v=1:1:1) electrolyte, Celgard2400 barrier film, be assembled into model
The button cell of LIR2016.
The charge-discharge test of button cell is carried out, often on Wuhan Jin Nuo Electronics Co., Ltd. LAND battery test system
Temperature condition, 0.1C constant current charge-discharge, charging/discharging voltage is limited in 0.005～1.5V.
Embodiment 1
The preparation method of a kind of lithium ion battery nano silicon-silica-based composite negative pole material, comprises the steps:
(1) it is the SiO of 50nm by median particle diameter2, the metal magnesium powder of 50 μm and the potassium chloride of 100 mesh sizes, according to quality
Mixing than 1:0.85:12, load in VC machine, arranging frequency is 30HZ, and the time is 40min.It is then sufficiently mixed uniform material
It is placed in reaction crucible, is passed through argon, be warming up to 950 DEG C, react 1h, the HCl solution of reacted product 1mol/L is soaked
Bubble 4h, centrifugal, it is washed with water after sucking filtration and washs 3 times, dry in 80 DEG C of vacuum drying ovens, obtain the nanometer titanium dioxide of nucleocapsid structure
Silicon-silicon grain.
(2) being placed in revolving burner by above-mentioned nano silicon-silicon grain, be passed through methane gas, flow is 0.1L/
Min, controlling revolving burner rotating speed is 0.8rpm, then heats to 1000 DEG C, is incubated 3h, obtains by nano silicon-silicon grain
The composite particles constituted with conductive carbon layer, wherein, conductive carbon layer is coated on the surface of nano silicon-silicon grain.
(3) being broken up by composite particles, carry out proportioning with the phenolic resin that granularity is 5 μm according to mass ratio 80:20, mixing is all
Even, it is subsequently placed in fusion machine, regulation rotating speed is 2000rpm, and cutter gap width is 0.5cm, merges 1h, obtains merging and produces
Thing, then joins in high temperature box furnace by fusion product, is passed through nitrogen protection gas, is warming up to 900 DEG C, after insulation 5h, obtains
Nano silicon-silica-based composite negative pole material.
The scanning of the nano silicon-silicon grain of the nucleocapsid structure that Fig. 2 is the embodiment of the present invention 1 to be prepared through step (1)
Ultramicroscope (SEM) picture, can be observed from figure, and nano silicon-silicon presents graininess, its particle mean size < 50nm.
Fig. 3 is the SEM figure of the nano silicon-silica-based composite negative pole material of the embodiment of the present invention 1 preparation, can from figure
Observing, this composite negative pole material granule is class ball shape, and individual particle is dispersed.
Fig. 4 is the XRD figure spectrum of the nano silicon-silica-based composite negative pole material of the embodiment of the present invention 1 preparation, from figure
Can be observed, the diffraction maximum of only nano-silicon in figure, the diffraction maximum of carbon almost without, this is primarily due to conductive carbon layer and carbon back
Matter is all amorphous cracking carbon.These external 20～30 ° also have a more weak diffraction bag, and this correspondence is the amorphous in material
The silicon dioxide of state exists.
Fig. 5 is that the nano silicon-silica-based composite negative pole material of the embodiment of the present invention 1 preparation is made battery and carries out electricity
Chemical property is tested, the first charge-discharge curve obtained, and as seen from the figure, this composite negative pole material first charge-discharge capacity is higher,
For 1250.0mAh/g, coulombic efficiency is 86% first.
Fig. 6 is that the nano silicon-silica-based composite negative pole material of the embodiment of the present invention 1 preparation is made battery and carries out electricity
Chemical property is tested, the cycle performance curve obtained, and as seen from the figure, this material has the cycle performance of excellence, circulates 100 weeks appearances
Amount conservation rate is 94.2%.
Powder body compacted density and the specific surface area data of the negative material of the present embodiment are shown in Table 1.
The negative material using the present embodiment makes battery, and the electrochemical performance data that test obtains is shown in Table 1.
Embodiment 2
The preparation method of a kind of lithium ion battery nano silicon-silica-based composite negative pole material, comprises the steps:
(1) it is the SiO of 160nm by median particle diameter2, the metallic sodium powder of 20 μm and the NaCl of 200 mesh sizes, according to mass ratio
1:0.5:8 mixes, and loads in VC machine, and arranging frequency is 20HZ, and the time is 1h.Then mixed material is placed in heat-treatment furnace,
It is passed through argon, is warming up to 750 DEG C, react 3h, the HCl solution of reacted product 1mol/L is soaked 2h, centrifugal, sucking filtration,
In vacuum drying oven, 80 DEG C of drying obtain the nano silicon-silicon grain of nucleocapsid structure.
(2) being placed in revolving burner by nano silicon-silicon grain, be passed through acetylene gas, flow is 0.3L/min, controls
Revolving burner rotating speed is 0.8rpm, then heats to 800 DEG C, is incubated 3h, obtains by nano silicon-silicon grain and conductive carbon layer
The composite particles constituted, wherein, conductive carbon layer is coated on the surface of nano silicon-silicon grain.
(3) being broken up by composite particles, carry out proportioning with the asphalt powder that granularity is 3 μm according to mass ratio 80:20, mixing is all
Even being placed in fusion machine, regulating frequency is 3000rpm, and cutter gap width is 1.0cm, mixes 0.5h, obtains fusion product,
Then fusion product is joined in high temperature box furnace, be passed through nitrogen protection gas, be warming up to 1000 DEG C, after insulation 6h, received
Rice silicon dioxide-silica-based composite negative pole material.
Powder body compacted density and the specific surface area data of the negative material of the present embodiment are shown in Table 1.
The negative material using the present embodiment makes battery, and the electrochemical performance data that test obtains is shown in Table 1.
Embodiment 3
The preparation method of a kind of lithium ion battery nano silicon-silica-based composite negative pole material, comprises the steps:
(1) it is the SiO of 20nm by median particle diameter2, the metal magnesium powder of 50 μm and 200 mesh KCl, mix according to mass ratio 1:1:8
Closing, load in VC machine, arranging frequency is 20HZ, and the time is 1h.Then mixed material is placed in heat-treatment furnace, is passed through argon,
It is warming up to 600 DEG C, reacts 6h, the HCl solution of reacted product 0.5mol/L is soaked 2h, centrifugal, sucking filtration, do in vacuum
In dry case, 80 DEG C of drying obtain the nano silicon-silicon grain of nucleocapsid structure.
(2) being placed in revolving burner by above-mentioned nano silicon-silicon grain, be passed through acetylene gas, flow is 1L/min,
Controlling revolving burner rotating speed is 0.8rpm/min, then heats to 900 DEG C, is incubated 6h, obtain by nano silicon-silicon grain and
The composite particles that conductive carbon layer is constituted, wherein, conductive carbon layer is coated on the surface of nano silicon-silicon grain.
(3) being broken up by composite particles, carry out proportioning with the asphalt powder that granularity is 5 μm according to mass ratio 80:20, mixing is all
Even, it is subsequently placed in fusion machine, regulating frequency is 500rpm, and cutter gap width is 0.01cm, mixes 0.25h, is merged
Product, then joins in high temperature box furnace by fusion product, is passed through nitrogen protection gas, is warming up to 1000 DEG C, after insulation 6h,
To nano silicon-silica-based composite negative pole material.
Powder body compacted density and the specific surface area data of the negative material of the present embodiment are shown in Table 1.
The negative material using the present embodiment makes battery, and the electrochemical performance data that test obtains is shown in Table 1.
Embodiment 4
The preparation method of a kind of lithium ion battery nano silicon-silica-based composite negative pole material, comprises the steps:
(1) it is the SiO of 20nm by median particle diameter2, the metallic aluminium powder of 30 μm and the NaCl of 200 mesh sizes, according to mass ratio
1:1:9 mixes, and loads in VC machine, and arranging frequency is 20HZ, and the time is 1h.Then mixed material is placed in heat-treatment furnace, logical
Enter argon, be warming up to 950 DEG C, react 2h, the HCl solution of reacted product 0.5mol/L is soaked 2h, centrifugal, sucking filtration,
In vacuum drying oven, 80 DEG C of drying obtain the nano silicon-silicon grain of nucleocapsid structure.
(2) being placed in revolving burner by above-mentioned nano silicon-silicon grain, be passed through acetylene gas, flow is 0.3L/
Min, controlling revolving burner rotating speed is 0.8rpm/min, then heats to 900 DEG C, is incubated 3h, obtains by nano silicon-silicon
The composite particles that grain and conductive carbon layer are constituted, wherein, conductive carbon layer is coated on the surface of nano silicon-silicon grain.
(3) composite particles is broken up, carry out proportioning with the epoxy powder that granularity is 2 μm according to mass ratio 80:20, mixed
Closing and be uniformly placed in fusion machine, regulating frequency is 1000rpm, and cutter, away from 0.5cm, mixes 2.0h, obtains fusion product, then will
Fusion product joins in high temperature box furnace, is passed through nitrogen protection gas, is warming up to 700 DEG C, after insulation 2h, obtains nanometer titanium dioxide
Silicon-silica-based composite negative pole material.
Powder body compacted density and the specific surface area data of the negative material of the present embodiment are shown in Table 1.
The negative material using the present embodiment makes battery, and the electrochemical performance data that test obtains is shown in Table 1.
Embodiment 5
The preparation method of a kind of lithium ion battery nano silicon-silica-based composite negative pole material, comprises the steps:
(1) it is the SiO of 30nm by median particle diameter2, the metal magnesium powder of 30 μm and the potassium chloride of 150 mesh sizes, according to quality
Mixing than 1:0.5:11, load in VC machine, arranging frequency is 25HZ, and the time is 1h.It is then sufficiently mixed uniform material to be placed in
In reaction crucible, it is passed through helium, is warming up to 850 DEG C, react 0.5h, the HCl solution of reacted product 5mol/L is soaked
2h, centrifugal, it is washed with water after sucking filtration and washs 3 times, dry in 90 DEG C of vacuum drying ovens, obtain the nanometer titanium dioxide of nucleocapsid structure
Silicon-silicon grain.
(2) above-mentioned nano silicon-silicon grain is placed in revolving burner, is passed through the gaseous mixture of methane and acetylene, stream
Amount is 0.8L/min, and controlling revolving burner rotating speed is 3rpm, then heats to 950 DEG C, is incubated 4.5h, obtains by nanometer titanium dioxide
The composite particles that silicon-silicon grain and conductive carbon layer are constituted, wherein, conductive carbon layer is coated on the table of nano silicon-silicon grain
Face.
(3) being broken up by composite particles, carry out proportioning with the phenolic resin that granularity is 3 μm according to mass ratio 80:20, mixing is all
Even, it is subsequently placed in fusion machine, regulation rotating speed is 2500rpm, and cutter gap width is 1cm, merges 5h, obtains fusion product,
Then fusion product is joined in high temperature box furnace, be passed through nitrogen protection gas, be warming up to 800 DEG C, after insulation 4h, obtain nanometer
Silicon dioxide-silica-based composite negative pole material.
Powder body compacted density and the specific surface area data of the negative material of the present embodiment are shown in Table 1.
The negative material using the present embodiment makes battery, and the electrochemical performance data that test obtains is shown in Table 1.
Comparative example 1
Except not carrying out step (1), and directly use silicon nanoparticle (particle diameter the is 120nm) replacement step (2) of commercialization
In nano silicon-silicon grain outside, other preparation methoies and condition are same as in Example 1.
Powder body compacted density and the specific surface area data of the composite of this comparative example are shown in Table 1.
The composite using this comparative example makes battery as negative pole, and the electrochemical performance data that test obtains is shown in Table 1.
Table 1
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element
Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1. nano silicon-silicon based composite material, it is characterised in that described composite includes carbon matrix and uniformly
Be dispersed in the composite particles in described carbon matrix, described composite particles include the nano silicon-silicon grain of nucleocapsid structure with
And it is coated on the conductive carbon layer on described nano silicon-silicon grain surface.
Nano silicon-silicon based composite material the most according to claim 1, it is characterised in that described composite
Median particle diameter is 1～45 μm, preferably 3～35 μm, more preferably 5～25 μm, particularly preferably 5～15 μm；
Preferably, the specific surface area of described composite is 1～55m2/ g, preferably 2～20m2/ g, more preferably 3～
15m2/g；
Preferably, the powder body compacted density of described composite is 0.4～2.6g/cm3, preferably 0.5～2.2g/cm3, enter one
Step is preferably 0.9～2g/cm3, particularly preferably 0.7～1.8g/cm3。
Nano silicon-silicon based composite material the most according to claim 1 and 2, it is characterised in that preferably, with institute
The gross mass stating composite is 100% meter, in described composite, the mass percent of described carbon matrix be 10～
60wt%, preferably 20～60wt%；
Preferably, it is in terms of 100% by the gross mass of described composite, in described composite, described nano silicon-silicon
The mass percent of core-shell structure particles is 5～80wt%；
Preferably, it is in terms of 100% by the gross mass of described composite, in described composite, the quality of described conductive carbon layer
Percentage ratio is 1～40wt%；
Preferably, described nano silicon-silicon grain is nucleocapsid structure, the kernel of described nano silicon-silicon grain and
Shell is respectively nanometer silicon dioxide particle and nanometer silicon layer；
Preferably, the particle diameter of described kernel nanometer silicon dioxide particle is 1～50nm；
Preferably, the thickness of described shell nanometer silicon layer is 5～40nm；
Preferably, the oxygen content of described nano silicon-silicon grain is 8～40wt%；
Preferably, the specific surface area of described nano silicon-silicon grain is 20～500m2/ g, preferably 50～400m2/g。
4., according to the preparation method of the nano silicon-silicon based composite material described in any one of claim 1-3, its feature exists
In, said method comprising the steps of:
(1) by nano-silicon oxide reducing agent and additive according to 1:(0.5～1): (1～12) mix, and are homogeneously combined, so
After-baking, then heat-treated products is washed and acid treatment, obtain the nano silicon-silicon grain of nucleocapsid structure；
(2) nano silicon-silicon grain in step (1) is carried out homogeneous in-situ carbon cladding, obtain by nano silicon-
The composite particles that silicon grain and conductive carbon layer are constituted, wherein, conductive carbon layer is coated on the surface of nano silicon-silicon grain；
(3) composite particles that step (2) obtains homogeneously is combined with carbon source, fusion treatment, then heat treatment, obtains nanometer titanium dioxide
Silicon-silicon based composite material.
The preparation method of nano silicon-silicon based composite material the most according to claim 4, it is characterised in that described
Method is additionally included in after step (3) heat treatment completes, and heat-treated products is pulverized, sieves and removed the step of magnetic.
6. according to the preparation method of the nano silicon-silicon based composite material described in claim 4 or 5, it is characterised in that step
Suddenly the chemical composition of (1) described nano-silicon oxide is SiOx, wherein 1≤X≤2；
Preferably, the median particle diameter of step (1) described nano-silicon oxide is 1～160nm；
Preferably, step (1) described reducing agent include in potassium, calcium, sodium, magnesium, aluminum, zinc, ferrum, copper or nickel any one or at least
The combination of two kinds；
Preferably, the median particle diameter of step (1) described reducing agent is 20～50 μm；
Preferably, the mass ratio of step (1) described nano-silicon oxide and described reducing agent is 1:(0.5～0.8)；
Preferably, step (1) described additive includes potassium chloride, potassium carbonate, potassium nitrate, potassium sulfate, sodium chloride, sodium carbonate, nitre
Any one or the combination of at least two in acid sodium or sodium sulfate；
Preferably, the screen cloth of 100～200 mesh is crossed before step (1) described additive uses；
Preferably, the mass ratio of step (1) described nano-silicon oxide and described additive is 1:(8～12)；
Preferably, step (1) is described to be homogeneously complex as: nano-silicon oxide, additive and reducing agent are homogeneously mixed,
To homogeneous mixture；
Preferably, the method that described homogeneous mixing uses includes that dry mixing methods and wet-mixed method, preferably dry method are mixed
Conjunction method；
Preferably, described dry mixing methods is dry ball milling method or is placed in the method carrying out in VC mixer mixing；
Preferably, the ball mill used in described dry ball milling method is planetary ball mill, high-speed stirred mill, tube mill, taper thread grinding
Any one in machine, rod mill and sand mill；
Preferably, being placed in VC mixer the method carrying out mixing described in is: by nano-silicon oxide, the reducing agent of step (1)
It is placed in VC mixer with additive, mixes, obtain homogeneous mixture；
Preferably, step (1) described heat treatment is: is placed in hermetic container by homogeneous mixture, enters under non-oxidizing atmosphere
Row heat treatment；
Preferably, in step (1) described heat treatment process, described non-oxidizing atmosphere is nitrogen atmosphere, hydrogen atmosphere, helium gas
Any one or the combination of at least two in atmosphere, argon gas atmosphere or neon atmosphere；
Preferably, the temperature of step (1) described heat treatment is 600～950 DEG C；
Preferably, the time of step (1) described heat treatment is 0.5～1h；
Preferably, step (1) described acid treatment is: be placed in container by heat-treated products, adds acid, processes；
Preferably, during step (1) described acid treatment, described in be processed as soak, or soak and with stirring；
Preferably, during step (1) described acid treatment, the time of described process is 1～8h, preferably 1～4h；
Preferably, during step (1) described acid treatment, described acid selected from hydrochloric acid, nitric acid, nitrous acid, sulphuric acid, sulfurous acid,
Any one or the combination of at least two in carbonic acid, boric acid, phosphoric acid, hydrocyanic acid, perchloric acid, acetic acid, benzoic acid or selenic acid；
Preferably, during step (1) described acid treatment, the concentration of described acid is 0.1～10mol/L；
Preferably, described method be additionally included in after step (1) acid treatment completes be centrifuged, sucking filtration and dry step.
7., according to the preparation method of the nano silicon-silicon based composite material described in any one of claim 4-6, its feature exists
In, the method that step (2) described homogeneous in-situ carbon cladding uses is in gas phase cladding, liquid phase coating method or solid phase cladding process
Any one, preferably gas phase cladding；
Preferably, using gas phase cladding to carry out homogeneous in-situ carbon cladding, described gas phase cladding is: to equipped with nanometer titanium dioxide
In the reacting furnace of silicon-silicon grain, be passed through gas phase carbon source, reacting furnace rotate under conditions of carry out in-situ deposition cladding, obtain by
The composite particles that nano silicon-silicon grain and conductive carbon layer are constituted, wherein, conductive carbon layer is coated on described nanometer titanium dioxide
The surface of silicon-silicon grain；
Preferably, in described gas phase cladding, described gas phase carbon source is methane, ethane, propane, ethylene, acetylene, propylene, gaseous state
Benzene, the toluene of gaseous state, the dimethylbenzene of gaseous state, the ethanol of gaseous state or gaseous state acetone in any one or the group of at least two
Close, the preferably combination of the toluene of methane, acetylene and gaseous state；
Preferably, in described gas phase cladding, the rotary speed of described reacting furnace is 0.2～8rpm；
Preferably, in described gas phase cladding, the flow that is passed through of described gas phase carbon source is 0.1～1.2L/min；
Preferably, in described gas phase cladding, described in-situ deposition cladding temperature be 600～1000 DEG C, preferably 800～
1000℃；
Preferably, in described gas phase cladding, the time of described in-situ deposition cladding is 3～6h.
8., according to the preparation method of the nano silicon-silicon based composite material described in any one of claim 4-7, its feature exists
It is any one in solid phase cladding process, liquid phase coating method or gas phase cladding in, the method for the described homogeneous Combined Mining of step (3)
Kind, preferably solid phase cladding process；
Step (3) described fusion treatment includes: add after composite particles step (2) obtained and carbon source mix homogeneously to merging
In machine, merge；
Preferably, during described fusion treatment, merge machine rotating speed be 600～3000rpm, preferably 300～
2000rpm；
Preferably, during described fusion treatment, the cutter gap merging machine is 0.01～1cm, preferably 0.1～0.3cm；
Preferably, during described fusion treatment, the time of fusion is at least 0.25h, preferably 0.25～8h, particularly preferably
It is 0.5～4h；
Preferably, step (3) described carbon source be selected from coal tar pitch and petroleum asphalt, mesophase pitch, coal tar, petroleum industry mink cell focus,
Heavy aromatic hydrocarbon, epoxy resin, phenolic resin, furfural resin, Lauxite, polyvinyl alcohol, polrvinyl chloride, Polyethylene Glycol, poly-
Any one or the combination of at least two in oxirane, Kynoar, acrylic resin or polyacrylonitrile；
Preferably, the particle diameter of step (3) described carbon source is 2～5 μm；
Preferably, step (3) described heat treatment process is connected with protection gas, described protection gas be nitrogen, helium, neon, argon or
Any one or the combination of at least two in Krypton；
Preferably, the temperature of step (3) described heat treatment is 700～1000 DEG C；
Preferably, the time of step (3) described heat treatment is 2～6h.
9. a negative material, it is characterised in that described negative material is the nanometer titanium dioxide that right wants described in any one of 1-3
Silicon-silicon based composite material.
10. a lithium ion battery, it is characterised in that described lithium ion battery comprises receiving described in any one of claim 1-3
Rice silicon dioxide-silicon based composite material is as the negative material of lithium ion battery.
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