CN109888240A - A kind of SiO with core-shell structurex- C composite negative pole material and preparation method thereof - Google Patents
A kind of SiO with core-shell structurex- C composite negative pole material and preparation method thereof Download PDFInfo
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- CN109888240A CN109888240A CN201910178475.2A CN201910178475A CN109888240A CN 109888240 A CN109888240 A CN 109888240A CN 201910178475 A CN201910178475 A CN 201910178475A CN 109888240 A CN109888240 A CN 109888240A
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Abstract
A kind of SiO with core-shell structurex- C composite negative pole material and preparation method thereof, the composite negative pole material include conductive kernel M, SiOxLayer, carbonaceous shell；Using SiOxGas in-situ deposition is wrapped in the surface conductive kernel M and forms conductive kernel M@SiOxThe core-shell structure of layer is wrapped in core-shell structure surface through pyrolytic reaction using carbon source precursor and constitutes carbonaceous shell；Preparation method includes: that conductive kernel is placed in the furnace with inert gas shielding；SiO is passed through into furnacexGas aggradation forms M@SiO on the surface of conductive kernelxCore-shell structure；After mixing by core-shell structure and carbon source presoma, pyrolytic reaction is carried out, the M@SiO with core-shell structure is obtainedx- C composite negative pole material.With the SiO of core-shell structure prepared by the present inventionxThe advantages of-C composite negative pole material is conductive high, initial coulomb efficiency is high, good cycling stability.Preparation process flow is simple, easily controllable, and synthesis cost is low, is suitble to large-scale production.
Description
Technical field
The present invention relates to a kind of lithium ion battery SiOx- C composite negative pole material and preparation method thereof, more particularly to one
Kind has the SiO of core-shell structurex- C composite negative pole material and preparation method thereof.Belong to composite material and electrochemical technology field.
Background technique
Lithium ion battery as a kind of environmentally protective new energy battery system, because its is environmental-friendly, can repeatedly charge and discharge,
The advantages that voltage is high, from it since nineteen ninety realizes commercialization for the first time, application field is related to side's aspect of human lives
Face, it is small to arrive mobile electronic device, power vehicle is arrived greatly, has all obtained unprecedented development.And with the expansion of its application range,
More stringent requirements are proposed for the energy density of lithium-ion battery system by the mankind.And current commercialized graphite cathode material pole
Big limits the exploitation and application of high performance lithium ion battery.Develop the novel cathode with high capacity, long circulation life
Material is the key that lithium ion battery is pushed further to develop.
In terms of numerous alternative negative electrode of lithium ion battery researchs, lithium storage content, suitable of the silica-base material because of its superelevation
Charging/discharging voltage platform, biggish earth reserves and by favor.However, the lower electric conductivity of silicon materials itself, charge and discharge
Huge volume expansion in journey, the problems such as surface solid electrolyte membrane is unstable, cause silicon materials circulation for several times after, tie
Structure avalanche and failure.To solve the above-mentioned problems, the method for modifying of mainstream has at present: the nanometer of silicon is combined to, prepared by porous
And composite structure design.However, the synthesis process of related nano-silicon and porous silicon, is related to expensive more and has
The silane of murder by poisoning, or be related to highly corrosive etching agent or preparation process height it is uncontrollable, lead to the nanometer prepared
Silicon materials pattern is not easy to control.And in the structure design aspect of silicon based composite material, thinking is to lead nano-silicon and other height
The material progress of electricity is compound, and is destroyed by constructing porous structure come structure of the volume expansion of capacity silicon to composite material.
However, related synthesis step is more tediously long, and used porous structure can also increase the generation of side reaction simultaneously, increase
The loss of lithium.It is still difficult to overcome in addition, silicon itself is up to stress problem caused by 400% volume expansion.The oxygen of silicon
Compound (SiOx, x ≈ 1) be silicon systems cathode a Typical Representative.This is because SiOxIn process of intercalation, there is lesser body
Product variation (~160%), more stable solid electrolyte membrane.In addition, in SiOxProcess of intercalation for the first time in, be formed by oxidation
Lithium and lithium metasilicate, the swelling stress that lithium ion transport can be accelerated respectively, buffer silicon.Therefore, using SiOxFor fast implementing
Silicon-based anode commercial applications have important practical significance.But due to SiOxPoor electron conduction, need by its with
High conductive material is compound active to improve its electrochemical reaction.But current preparation method is generally to use SiOxWith other
Mutually by the method for ball milling, prepared composite material has that two-phase is unevenly distributed, grain graininess is difficult to control, sternly
The electrochemical stability of composite material is affected again.
Think after present patent application person's research, the graphite cathode of current lithium-ion battery system has arrived at the pole of application
Limit, is still difficult to solve by the good huge volume expansion of silicium cathode.Thus, with high capacity, lower volume expansion
SiOxIt is the negative electrode material of great potential.But SiOxThe problem of there are still poorly conductives, and nanoscale SiOxPreparation difficulty
It is larger.Therefore, there is highly conductive, high stability SiOxThe short route of composite negative pole material, low cost are prepared for pushing silicon
The commercialization process of base cathode is of great significance.
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of SiO with core-shell structurex- C composite negative pole
Material uses the cathode material so that prepared composite material has high structural stability and electrochemical cycle stability
The capacity of the lithium ion battery of material preparation, cycle performance, high rate performance, service life are higher than common graphite and silicon-carbon cathode material
Material,
A kind of process is simple, preparation cost is cheap, can advise greatly to provide for second technical problem to be solved by this invention
Mould production, the SiO with good commercial applications prospectxThe preparation method of-C composite negative pole material.
A kind of SiO with core-shell structure of the present inventionx- C composite negative pole material, the composite negative pole material include in conduction
Core M, SiOxLayer, carbonaceous shell；Using SiOxGas in-situ deposition is wrapped in the surface conductive kernel M and constitutes SiOxLayer is formed conductive
Kernel M@SiOxThe core-shell structure of layer, the carbonaceous shell are wrapped in core-shell structure surface structure through pyrolytic reaction by carbon source precursor
At；SiOxIn, 0.75≤x≤1.25.
A kind of SiO with core-shell structure of the present inventionx- C composite negative pole material, it is described conduction kernel selected from silicon, graphite, in
Between one of phase carbosphere, carbon black, carbon ball, carbon fiber, carbon nanotube, metal and its compound with electric action or more
Kind；Metal is selected from least one of copper powder, silver powder, bronze etc., metallic compound be metal sulfide with electric action,
At least one of oxide, carbide, nitride etc. compound；The granularity of conductive kernel is 20nm~15 μm.
A kind of SiO with core-shell structure of the present inventionx- C composite negative pole material, SiOxGas in-situ deposition technological parameter are as follows:
1300-1800 DEG C of gas temperature, gas flow rate 20-500ml/min；The temperature of conductive kernel is 200~400 DEG C.
A kind of SiO with core-shell structure of the present inventionx- C composite negative pole material, conductive kernel M and the SiO depositedxMatter
Amount is than being 1:0.1~5.
A kind of SiO with core-shell structure of the present inventionx- C composite negative pole material, the carbon source presoma are pitch, phenolic aldehyde
One of resin, glucose, high molecular polymer, methane, ethane are a variety of.
A kind of SiO with core-shell structure of the present inventionx- C composite negative pole material, pyrolytic reaction technological parameter are as follows: temperature is
500~900 DEG C, the reaction time be 2~8h, reaction atmosphere be one of argon gas, hydrogen, nitrogen, helium protective atmosphere or
It is a variety of.
A kind of SiO with core-shell structure of the present inventionx- C composite negative pole material, the quality of carbon source presoma and core-shell structure
Than for 1:4~30.
A kind of SiO with core-shell structure of the present inventionxThe preparation method of-C composite negative pole material, comprising the following steps:
Step 1: being placed in powdered conductive kernel M in the furnace with inert gas shielding；SiO is passed through into furnacexGas
Body, control in-furnace temperature are 200~400 DEG C, make SiOxIt is deposited on the surface of conductive kernel M, forms M@SiOxCore-shell structure；
Step 2: by M@SiOxCore-shell structure and carbon source presoma after mixing, carry out being pyrolyzed in 500~900 DEG C anti-
It answers, obtains the M@SiO with core-shell structurex- C composite negative pole material.
A kind of SiO with core-shell structure of the present inventionxThe preparation method of-C composite negative pole material, the SiOxGas is
It is obtained by the vacuum thermal response of silicon and silica, vacuum thermal reaction process parameter are as follows:
The mass ratio of silicon and silica is 1:1.6-2.7, and the reaction temperature of silicon and silica is 1300~1800 DEG C,
Reaction vacuum degree is 1~500Pa, and the reaction time is 2~15h；Obtain SiOxGas, in which: 0.75≤X≤1.25.
A kind of SiO with core-shell structure of the present inventionxThe preparation method of-C composite negative pole material, the conductive kernel M
Selected from silicon, graphite, carbonaceous mesophase spherules, carbon black, carbon ball, carbon fiber, carbon nanotube, metal and its with the chemical combination of electric action
One of object is a variety of；Metal is selected from least one of copper powder, silver powder, bronze etc., and metallic compound is to make with conduction
At least one of metal sulfide, oxide, carbide, nitride etc. compound；The granularity of conductive kernel M is 20nm
~15 μm；Conductive kernel and the SiO depositedxMass ratio be 1:0.1~5.
A kind of SiO with core-shell structure of the present inventionxThe preparation method of-C composite negative pole material, inert atmosphere is selected from furnace
One of argon gas, hydrogen, nitrogen, helium are a variety of.
A kind of SiO with core-shell structure of the present inventionxThe preparation method of-C composite negative pole material, the carbon source presoma
Selected from one of pitch, phenolic resin, glucose, high molecular polymer, methane, ethane or a variety of；Pyrolytic reaction technique ginseng
Number are as follows: reaction temperature is 500~900 DEG C, and heating time is 2~8h, and reaction atmosphere is in argon gas, hydrogen, nitrogen, helium
It is one or more；The mass ratio of carbon source presoma and core-shell structure is 1:4~30.
The SiO with core-shell structure by adopting the above technical schemex- C composite negative pole material and preparation method thereof, kernel
For the material of conductive energy, can be with the active metal oxide of electrochemical reaction, metal sulfide, silicon, graphite
Deng being also possible to the inert particle of electrochemical reaction, such as copper powder, carbon black, silicon carbide；SiOxCompound with conductive kernel is logical
Cross SiO caused by the vacuum thermal response of silicon and silicaxGas conductive substrates surface in-situ deposition and formed, guarantee
The two compound uniformity and validity；Its external further carbonaceous shell protection of progress, is to improve material internal
Electronic transmission performance, while carbonaceous shell can buffer SiOxVolume expansion brought by structural stress, improve composite wood
The structural stability of material.In addition, carbonaceous shell can optimize the surface nature of composite material, be conducive in electrochemical reaction process
It is middle to form stable solid electrolyte membrane.Therefore, in final prepared composite material, SiOxIt is to be dispersed in conduction
The surface of core, the protection of outer layer carbonaceous shell can play improve electric conductivity, improve composite structure stability, improve it is compound
The multiple action of the surface characteristic of material.Compared with prior art, the present invention having the advantage that
①SiOxIt is that uniform deposition does not need at additional ball milling on the surface of conductive substrates by way of in-situ deposition
Reason, and can be regulated and controled by adjusting the partial size of the Size on Composite of kernel；
2. selected inner nuclear material is conductive, active path can be provided for electron-transport, solve SiOxIt leads
Electrically poor problem, to improve the chemical property of composite material；
3. selected carbonaceous substrate is pyrolytic carbon, carbon substrate can not only receive SiOxVolume expansion to guarantee structure
Stability, and help to form stable solid electrolyte membrane on the surface of composite material by the modification of pyrolytic carbon, into one
Step prevents infiltration of the electrolyte to composite inner, ensure that the good structural stability of composite material, high coulombic efficiency
And good electrochemical stability；In addition, its good electric conductivity and possessed embedding de- lithium characteristic, it helps improve composite wood
The high rate performance and specific capacity of material；
4. composite material preparation flow is simple, is easy to large-scale production.
In conclusion with the SiO of core-shell structure prepared by the present inventionx- C composite negative pole material has conductive
The advantages of height, initial coulomb efficiency height, good cycling stability.Through SiO prepared by the present inventionx- C composite negative pole material, electricity
Subconductivity rate is higher than 0.01S/cm, and the reversible capacity that initial coulomb efficiency is higher than under 82%, 0.2C multiplying power after 100 circle of circulation is kept
Rate is higher than 85%.Preparation process flow is simple, at low cost, is suitble to large-scale production.
Detailed description of the invention
Attached drawing 1 is composite negative pole material structural schematic diagram of the invention.
Attached drawing 2 is CB@SiO prepared by the embodiment of the present invention 1xThe scanning electron microscope (SEM) photograph of composite material.
Attached drawing 3 is CB@SiO prepared by the embodiment of the present invention 1xThe scanning electron microscope (SEM) photograph of@C composite negative pole material.
Attached drawing 4 is CB@SiO prepared by the embodiment of the present invention 1xThe transmission electron microscope picture of@C composite negative pole material.
From attached drawing 2 it can be seen that gained CB@SiOxComposite material exhibits be it is spherical, radial dimension be 100~200nm,
And it can be seen that its core-shell structure；
Attached drawing 3 is it can be seen that gained CB@SiOx@C composite negative pole material particle be it is spherical, radial dimension be 200~
300nm；
Attached drawing 4 is it can be seen that gained CB@SiOx@C composite negative pole material shows apparent core-shell structure.
Inner nuclear material used by embodiment 1 is commercialized carbon black powders, its own is formed by Compound Negative to be spherical
Pole material can still keep spherical.
Specific embodiment
Invention is further described in detail combined with specific embodiments below, but the invention is not limited to following implementations
Example.
The conductivity of powder is measured using four probe method in the embodiment of the present invention, comparative example, resulting materials library for the first time
Logical sequence efficiency and specific capacity conservation rate are by being coated resulting materials, after button cell assembly, in button cell electrochemistry
It is measured on tester.
Embodiment 1:
(1) 100g carbon black powders (CB) are placed in the tube furnace of argon gas protection, in-furnace temperature is kept for 250 DEG C；
(2) it after 28g silicon powder being uniformly mixed and is compacted with 60g silicon dioxide powder, is placed in vacuum tube furnace, keeps in furnace
Vacuum degree is 50Pa, and tube furnace is warming up to 1350 DEG C, keeps the temperature 5h；And by the SiO of generationxGas is passed into the tubular type of step
Surface deposition is carried out in furnace, gas flow rate 20ml/min obtains CB@SiOxComposite material；
(3) by 20g glucose and 10gCB@SiOxAfter mixing, it is placed in tube furnace, is passed through nitrogen atmosphere protection, and
800 DEG C, soaking time 6h are warming up to, CB@SiO is obtainedx@C composite negative pole material.
Show gained CB@SiO through the test of four probesxThe electronic conductivity of@C composite negative pole material is 0.18S/cm；Electrification
Learn test show its initial coulomb efficiency be under 86%, 0.2C multiplying power circulation 100 enclose after reversible capacity conservation rate be 88%.
Embodiment 2:
(1) 50g artificial graphite powder (AG) is placed in the tube furnace of nitrogen protection, in-furnace temperature is kept for 300 DEG C；
(2) it after 28g silicon powder being uniformly mixed and is compacted with 66g silicon dioxide powder, is placed in vacuum tube furnace, keeps in furnace
Vacuum degree is 20Pa, and tube furnace is warming up to 1450 DEG C, keeps the temperature 4h；And by the SiO of generationxGas is passed into the tubular type of step
Surface deposition is carried out in furnace, gas flow rate 50ml/min obtains AG@SiOxComposite material；
(3) by 20g pitch and 10g AG@SiOxAfter mixing, it is placed in tube furnace, is passed through nitrogen atmosphere protection, and
850 DEG C, soaking time 6h are warming up to, AG@SiO is obtainedx@C composite negative pole material.
Show gained AG@SiO through the test of four probesxThe electronic conductivity of@C composite negative pole material is 0.21S/cm；Electrification
Learn test show its initial coulomb efficiency be under 89%, 0.2C multiplying power circulation 100 enclose after reversible capacity conservation rate be 92%.
Embodiment 3:
(1) by 50g titanium dioxide (TiO2) be placed in the tube furnace of nitrogen protection, in-furnace temperature is kept for 300 DEG C；
(2) it after 28g silicon powder being uniformly mixed and is compacted with 58g silicon dioxide powder, is placed in vacuum tube furnace, keeps in furnace
Vacuum degree is 50Pa, and tube furnace is warming up to 1350 DEG C, keeps the temperature 4h；And by the SiO of generationxGas is passed into the tubular type of step
Surface deposition is carried out in furnace, gas flow rate 200ml/min obtains TiO2@SiOxComposite material；
(3) by 15g pitch and 10g TiO2@SiOxAfter mixing, it is placed in tube furnace, is passed through nitrogen atmosphere protection, and
800 DEG C are warming up to, soaking time 5h obtains TiO2@SiOx@C composite negative pole material.
Show gained TiO through the test of four probes2@SiOxThe electronic conductivity of@C composite negative pole material is 0.21S/cm；Electricity
Test chemical shows that its initial coulomb efficiency is for the reversible capacity conservation rate after 100 circle of circulation under 91%, 0.2C multiplying power
92%.
Embodiment 4:
(1) 10g carbon nanotube (CNTs) is placed in the tube furnace of nitrogen protection, in-furnace temperature is kept for 400 DEG C；
(2) it after 28g silicon powder being uniformly mixed and is compacted with 65g silicon dioxide powder, is placed in vacuum tube furnace, keeps in furnace
Vacuum degree is 400Pa, and tube furnace is warming up to 1450 DEG C, keeps the temperature 6h；And by the SiO of generationxGas is passed into the pipe of step
Surface deposition is carried out in formula furnace, gas flow rate 20ml/min obtains CNTs@SiOxComposite material；
(3) 16g CNTs@SiO is takenxIt is placed in tube furnace, is passed through the mixed atmosphere of methane and hydrogen, and be warming up to 800
DEG C, soaking time 6h obtains CNTs@SiOx@C composite negative pole material.
Show gained CNTs@SiO through the test of four probesxThe electronic conductivity of@C composite negative pole material is 0.68S/cm；Electricity
Test chemical shows that its initial coulomb efficiency is for the reversible capacity conservation rate after 100 circle of circulation under 94%, 0.2C multiplying power
93%.
Embodiment 5:
(1) 10g graphene (G) is placed in the tube furnace of nitrogen protection, in-furnace temperature is kept for 300 DEG C；
(2) it after 28g silicon powder being uniformly mixed and is compacted with 57g silicon dioxide powder, is placed in vacuum tube furnace, keeps in furnace
Vacuum degree is 5Pa, and tube furnace is warming up to 1350 DEG C, keeps the temperature 5h；And by the SiO of generationxGas is passed into the tubular type of step
Surface deposition is carried out in furnace, gas flow rate 100ml/min obtains G@SiOxComposite material；
(3) by 15g pitch and 15g G@SiOxAfter mixing, it is placed in tube furnace, is passed through nitrogen/hydrogen gaseous mixture
Atmosphere protection, and 750 DEG C are warming up to, soaking time 4h obtains G@SiOx@C composite negative pole material.
Show gained G@SiO through the test of four probesxThe electronic conductivity of@C composite negative pole material is 0.46S/cm；Electrification
Learn test show its initial coulomb efficiency be under 92%, 0.2C multiplying power circulation 100 enclose after reversible capacity conservation rate be 95%.
Comparative example 1: it is added without kernel
(1) it after 28g silicon powder being uniformly mixed and is compacted with 60g silicon dioxide powder, is placed in vacuum tube furnace, keeps in furnace
Vacuum degree is 50Pa, and tube furnace is warming up to 1350 DEG C, keeps the temperature 5h；Collect SiO generatedxGas obtains SiO through coolingxBlock
Body material；
(2) by above-mentioned SiOxBlock materials, which are placed in planetary ball mill, carries out abundant ball-milling treatment, obtains SiOxPowder；
(3) by 20g glucose and 10gSiOxPowder after mixing, is placed in tube furnace, is passed through nitrogen atmosphere protection,
And 800 DEG C are warming up to, soaking time 6h obtains SiOx@C composite negative pole material.
Show gained SiO through the test of four probesxThe electronic conductivity of@C composite negative pole material is 0.17S/cm；Electrochemistry
Test show its initial coulomb efficiency be under 68%, 0.2C multiplying power circulation 100 circle after reversible capacity conservation rate be 49%.
Comparative example 2: it is protected without carbonaceous shell
(1) 50g artificial graphite powder (AG) is placed in the tube furnace of nitrogen protection, in-furnace temperature is kept for 250 DEG C；
(2) it after 28g silicon powder being uniformly mixed and is compacted with 60g silicon dioxide powder, is placed in vacuum tube furnace, keeps in furnace
Vacuum degree is 50Pa, and tube furnace is warming up to 1450 DEG C, keeps the temperature 4h；And by the SiO of generationxGas is passed into the tubular type of step
Surface deposition is carried out in furnace, obtains AG@SiOxComposite material.
Show gained AG@SiO through the test of four probesxThe electronic conductivity of composite negative pole material is 0.003S/cm；Electrification
Learn test show its initial coulomb efficiency be under 62%, 0.2C multiplying power circulation 100 enclose after reversible capacity conservation rate be 37%.
By comparing the measured data of embodiment 1-5 and comparative example 1,2, it can be deduced that: it, can be effective by adding kernel
By SiOxGas is uniformly grown in the surface of inner nuclear material, and by the pattern and size of control kernel, adjusts final
The pattern and size of product；By the protection of outer layer carbonaceous shell, the conductivity of composite material can be effectively improved, and excellent
The exterior surface features for changing composite material, improve the chemical property of composite material.
Claims (10)
1. a kind of SiO with core-shell structurex- C composite negative pole material, the composite negative pole material include conductive kernel M, SiOx
Layer, carbonaceous shell；Using SiOxGas in-situ deposition is wrapped in the surface conductive kernel M and constitutes SiOxLayer forms conduction kernel M@
SiOxThe core-shell structure of layer, the carbonaceous shell are wrapped in core-shell structure surface through pyrolytic reaction by carbon source precursor and constitute；SiOx
In, 0.75≤x≤1.25.
2. a kind of SiO with core-shell structure according to claim 1x- C composite negative pole material, it is characterised in that: described
Conductive kernel M is selected from silicon, graphite, carbonaceous mesophase spherules, carbon black, carbon ball, carbon fiber, carbon nanotube, metal and its has conduction
One of compound of effect is a variety of；The granularity of conductive kernel is 20nm~15 μm.
3. a kind of SiO with core-shell structure according to claim 2x- C composite negative pole material, it is characterised in that: described
Metal is selected from least one of copper powder, silver powder, bronze, and metallic compound is the metal sulfide with electric action, oxidation
At least one of object, carbide, nitride compound.
4. a kind of SiO with core-shell structure according to claim 1x- C composite negative pole material, it is characterised in that: SiOx
Gas in-situ deposition technological parameter are as follows: 1300-1800 DEG C of gas temperature；The temperature of conductive kernel M is 200~400 DEG C；In conduction
The core M and SiO depositedxMass ratio be 1:0.1~5.
5. a kind of SiO with core-shell structure according to claim 1x- C composite negative pole material, it is characterised in that: described
Carbon source presoma is one of pitch, phenolic resin, glucose, high molecular polymer, methane, ethane or a variety of.
6. a kind of SiO with core-shell structure according to claim 5x- C composite negative pole material, it is characterised in that: pyrolysis
Reaction process parameter are as follows: temperature is 500~900 DEG C, and reaction atmosphere is argon gas, hydrogen, nitrogen, one in helium protective atmosphere
Kind is a variety of；The mass ratio of carbon source presoma and core-shell structure is 1:4~30.
7. a kind of SiO with core-shell structurexThe preparation method of-C composite negative pole material, comprising the following steps:
Step 1: being placed in powdered conductive kernel M in the furnace with inert gas shielding；SiO is passed through into furnacexGas, control
In-furnace temperature is 200~400 DEG C, makes SiOxIt is deposited on the surface of conductive kernel M, forms M@SiOxCore-shell structure；
Step 2: by M@SiOxCore-shell structure and carbon source presoma after mixing, in 500~900 DEG C of progress pyrolytic reactions, obtain
To the M@SiO with core-shell structurex- C composite negative pole material.
8. a kind of SiO with core-shell structure according to claim 7xThe preparation method of-C composite negative pole material, feature
It is: the SiOxGas is obtained by the vacuum thermal response of silicon and silica, vacuum thermal reaction process parameter are as follows:
The mass ratio of silicon and silica is 1:1.6-2.7, and the reaction temperature of silicon and silica is 1300~1800 DEG C, reaction
Vacuum degree is 0.5~500Pa, obtains SiOxGas, in which: 0.75≤x≤1.25.
9. a kind of SiO with core-shell structure according to claim 7xThe preparation method of-C composite negative pole material, feature
Be: the conductive kernel M be selected from silicon, graphite, carbonaceous mesophase spherules, carbon black, carbon ball, carbon fiber, carbon nanotube, metal and
One of its compound with electric action is a variety of；Metal is selected from least one of copper powder, silver powder, bronze etc., gold
Belonging to compound is at least one of metal sulfide with electric action, oxide, carbide, nitride compound；It leads
The granularity of electric kernel M is 20nm~15 μm；Conductive kernel and the SiO depositedxMass ratio be 1:0.1~5.
10. a kind of SiO with core-shell structure according to claim 7xThe preparation method of-C composite negative pole material, it is special
Sign is: the carbon source presoma in pitch, phenolic resin, glucose, high molecular polymer, methane, ethane one
Kind is a variety of；Pyrolytic reaction technological parameter are as follows: reaction temperature be 500~900 DEG C, reaction atmosphere be selected from argon gas, hydrogen, nitrogen,
One of helium is a variety of；The mass ratio of carbon source presoma and core-shell structure is 1:4~30.
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