CN109273680A - A kind of porous silicon-carbon cathode material and preparation method thereof and lithium ion battery - Google Patents

A kind of porous silicon-carbon cathode material and preparation method thereof and lithium ion battery Download PDF

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CN109273680A
CN109273680A CN201810998286.5A CN201810998286A CN109273680A CN 109273680 A CN109273680 A CN 109273680A CN 201810998286 A CN201810998286 A CN 201810998286A CN 109273680 A CN109273680 A CN 109273680A
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porous silicon
sio
carbon
porous
conductive agent
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CN109273680B (en
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叶柏青
张蕾
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Danfu Sichuan West Energy Science And Technology Ltd Co
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Danfu Sichuan West Energy Science And Technology Ltd Co
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 present invention relates to lithium ion battery material technical field more particularly to a kind of porous silicon-carbon cathode material and preparation method thereof and lithium ion battery, which includes porous silicon carbon material and graphite material；The porous silicon carbon material is core-shell type three-layer composite structure, including kernel and is successively coated on the middle layer and outermost layer of kernel, and the kernel is noncrystalline, porous silicon oxygen material SiOx, the middle layer is reticulated conductive agent clad, and the outermost layer is amorphous carbon coating layer.Compared with the prior art, the present invention is designed by core-shell type three-layer composite structure, so that the volume expansion of the porous silicon carbon material substantially reduces, first charge discharge efficiency and cycle performance are significantly improved；And after mixing with graphite material, the porous silicon-carbon cathode material reversible specific capacity >=487.8mAh/g, first charge discharge efficiency >=87.86% for the first time recycle 500 capacity retention ratio >=94.6%, cubical expansivity≤19.51%.

Description

A kind of porous silicon-carbon cathode material and preparation method thereof and lithium ion battery
Technical field
The present invention relates to lithium ion battery material technical field more particularly to a kind of porous silicon-carbon cathode material and its preparations Method and lithium ion battery.
Background technique
Energy density is high, have a safety feature, cycle performance is good, memory-less effect, operating voltage because having for lithium ion battery The advantages that high, environmental-friendly, self discharge is small and be widely used in every field.It is issued as National Ministry of Finance announces " notice of fiscal support policy is promoted and applied about 2016-2020 new-energy automobile ", it is desirable that lithium ion battery has higher Energy density, and lithium ion battery energy density size is mainly influenced by positive and negative anodes active material, and commercialization is answered at present Negative electrode active material is mainly artificial graphite, but its current actual specific capacity is already close to its theoretical specific capacity 372mAh/g, it is difficult to there is room for promotion again, and requirement of the lithium ion battery to energy density is higher and higher, develops new high energy Metric density material is extremely urgent.
Silicon materials are because having high theoretical specific capacity (4200mAh/g) and resource abundant and lower de- lithium current potential (< 0.5V) will be one of the effective material for substituting graphite.However, silicon materials exist during the insertion of lithium ion and abjection Huge volume change and lower first charge discharge efficiency and very poor cycle performance, it is difficult to realize actual production application.
For the above problem, occur the method for modifying much about silica-base material, such as three-dimensional porous Si at present Grain, nucleocapsid crystalline substance/amorphous Si nano wire, Si- metal oxide be compound, Si- carbon core-shell structure and graphene are as buffering etc..On Although stating scheme to have some improvement to the expansion of silica-base material, modification mode is more single, and effect is unobvious, still remains The problems such as preparation is difficult, electrical contact is poor, with high costs, and compared with graphite material, first charge discharge efficiency, cycle performance, body Product expansion rate still has biggish gap, needs further to be promoted.
Authorization Notice No. is that the Chinese invention patent of CN 102903896B discloses a kind of silicon-carbon for lithium ion battery Composite negative pole material, preparation method and application, the negative electrode material are core-shell structure, including nucleome and are successively coated on nucleome Middle layer and outermost layer, the nucleome are nano-silicon, and the middle layer is agraphitic carbon, and the outermost layer is 1-dimention nano carbon materials Material, but the expansion rate of the silicon-carbon composite cathode material is higher, its conductivity, cycle performance etc. is caused still to need further to be mentioned It is high.
Summary of the invention
It is an object of the present invention to: in view of the deficiencies of the prior art, and a kind of porous silicon-carbon cathode material is provided, with Solve the problems, such as that existing silicon based anode material first charge discharge efficiency is low, volume expansion is big, poor circulation.
The second object of the present invention is: providing a kind of preparation method of porous silicon-carbon cathode material.
The third object of the present invention is: providing a kind of lithium ion battery.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of porous silicon-carbon cathode material, including porous silicon carbon material and graphite material；The porous silicon carbon material is core Shell structure, including kernel and is successively coated on the middle layer and outermost layer of kernel, and the kernel is noncrystalline, porous silicon oxygen material SiOx, wherein 0 x≤2 <, the middle layer are reticulated conductive agent clad, and the outermost layer is amorphous carbon coating layer.
Preferably, the porous silicon oxygen material SiOxPorosity be 20~80%, more preferably 40~80%.The hole SiO can be effectively controlled in rangexVolume expansion allows its expansion to fill using the hole of itself.It, can not if porosity is too low Effectively control SiOxVolume expansion；If porosity is excessively high, SiO will affectxStructural stability.
Preferably, the porous silicon oxygen material SiOxMedian particle diameter D50It is 3~7 μm.
Preferably, the conductive agent clad with a thickness of 10~100nm, the conductive agent includes conductive agent A and conduction Agent B, the conductive agent A are at least one of carbon nanotube, graphene, and the conductive agent B is conductive black.Wherein, conductive agent Clad is in porous SiOxSurface is formed using conductive black as node, and carbon nano tube/graphene is the conductive network for connecting network Clad structure.
Preferably, the amorphous carbon coating layer with a thickness of 0.5~2 μm, the amorphous carbon is asphalt, coal tar One or more of oil asphalt is formed after being carbonized.
Preferably, the mass ratio of the porous silicon carbon material and the graphite material is 5~50%:50~95%；It is described Porous silicon oxygen material SiOx, the conductive agent and the amorphous carbon mass ratio be 20~50%:5~20%:30~75%.
Preferably, the graphite material is natural graphite, in artificial graphite, micro crystal graphite, carbonaceous mesophase spherules, soft carbon It is at least one.
The present invention also provides a kind of preparation methods of porous silicon-carbon cathode material, comprising the following steps:
Step 1), by Si oxide SiOxIn the mass ratio of the material be (0.5~2) with active metal powder: 1 ratio is mixed It closes, 1~4h of ball milling is uniformly mixed it in ball grinder, under an inert atmosphere 650~1000 DEG C of heat treatments 4~for 24 hours, through broken Classification obtains D50For 3~7 μm of Si oxide SiOxAnd metal oxide composite, wherein 0 x≤2 <；
Step 2) carries out pickling to material prepared by step 1) using hydrochloric acid, removes metal oxide, further wash, It is dried to obtain porous SiOxMaterial；
Conductive agent A and conductive agent B using dispersing agent are (1~20) by step 3) in mass ratio: 1 is configured to uniformly lead Electric agent solution, wherein conductive agent A is at least one of carbon nanotube, graphene, and conductive agent B is conductive black；
Step 4), the porous SiO for preparing step 2)xMaterial is added in the conductive agent solution of step 3) preparation, porous SiOx The molar ratio of material and conductive agent is 10:(0.5~2), 0.5~3h is stirred under the mixing speed of 500~1500r/min, is made It is uniformly mixed, and vacuum drying removes solvent, obtains the porous SiO of surface coated with conductive agentxParticle；
Step 5), the coated with conductive agent for preparing pitch and step 4) porous SiOxParticle is (1~5) in mass ratio: 1 Ratio mixing, ball milling merges 1~3h, is heated to 260~270 DEG C of completion under an inert atmosphere and coats, be continuously heating to 500~ 600 DEG C are completed preliminary carbonization, then are warming up to 1000~1100 DEG C of high temperature cabonizations 8~for 24 hours, obtain the porous silicon of three-layer nuclear shell structure Carbon material；
Step 6), porous silicon carbon material prepared by step 5) and graphite material are 5~50%:50~95% in mass ratio Ratio mixing, 1~4h of ball milling is uniformly mixed it to get to porous silicon-carbon cathode material in ball grinder.
Preferably, in step 1), the active metal powder is one or more of magnesium, zinc, iron.
Preferably, in step 1), the Si oxide SiOxWith the mass ratio of the material of active metal powder be (0.8~ 1.2): 1.If active metal powder additive amount is very few, the pore structure generated is very few, and it is swollen can not to effectively reduce material volume It is swollen；If active metal powder additive amount is excessive, the pore structure generated is excessive, can reduce the structural strength of material and be compacted close Degree.
Preferably, in step 1) and step 5), the inert atmosphere is one of nitrogen, argon gas, helium.
Preferably, in step 2), the porous silicon oxygen material SiOxPorosity be 20~80%, more preferably 40~ 80%.SiO can be effectively controlled in the aperture rangesxVolume expansion allows its expansion to fill using the hole of itself.If porosity It is too low, then it can not effectively control SiOxVolume expansion；If porosity is excessively high, SiO will affectxStructural stability.
Preferably, in step 3), the dispersing agent is polyvinylpyrrolidone (PVP).
Preferably, in step 3), the carbon nanotube is single-walled carbon nanotube, multi-walled carbon nanotube, single-walled carbon nanotube One or more of conduction liquid, multi-walled carbon nanotube conduction liquid.
Preferably, in step 4), the vacuum drying temperature is 60~150 DEG C, and drying time is 1~3h.
Preferably, in step 5), the pitch is one or more of asphalt, coal tar asphalt.
Preferably, in step 6), the graphite material is that natural graphite, artificial graphite, micro crystal graphite, mesocarbon are micro- At least one of ball, soft carbon.
The present invention also provides a kind of lithium ion batteries, including porous silicon-carbon cathode material described in any of the above-described section.
The beneficial effects of the present invention are: a kind of porous silicon-carbon cathode material of the present invention, including porous silicon carbon material and stone Ink material；The porous silicon carbon material is core-shell type three-layer composite structure, including kernel and is successively coated on the middle layer of kernel And outermost layer, the kernel are noncrystalline, porous silicon oxygen material SiOx, the middle layer be reticulated conductive agent clad, it is described most Outer layer is amorphous carbon coating layer.Wherein, porous SiOxKernel reacts to form Li in embedding lithium for the first time4SiO4, effectively buffered silicon material The Volumetric expansion of material, the reserved space of porous structure can inhale volume change of the material in charge and discharge process It receives, reduces the volume change of material entirety；Conductive agent clad is coated on porous SiO with web formxSurface, led in raising While electrical, reticular structure limits porous SiOxInterior Assessment of Nuclear Volume expands outward；The effect of outermost amorphous carbon coating layer It is to form uniform and stable SEI film, while avoids electrolyte and porous SiOxThe contact of kernel and it is limited to external expansion. Therefore, it is designed by core-shell type three-layer composite structure, the volume expansion of the porous silicon carbon material substantially reduces, first charge discharge efficiency and follows Ring performance is significantly improved；And after being mixed with graphite material, the porous silicon-carbon cathode material for the first time reversible specific capacity >= 487.8mAh/g, first charge discharge efficiency >=87.86% recycle 500 capacity retention ratio >=94.6%, cubical expansivity≤19.51%.
Detailed description of the invention
Fig. 1 is the porous silicon carbon material preparation method schematic diagram of the present invention.
Fig. 2 is scanning electron microscope (SEM) photograph of the obtained porous silicon-carbon cathode material under 1k enlargement ratio in embodiment 1.
Fig. 3 is the first charge-discharge curve graph of obtained porous silicon-carbon cathode material in embodiment 1.
Fig. 4 is charge and discharge cycles of the obtained porous silicon-carbon cathode material under 0.5C charge-discharge magnification in embodiment 1 Curve graph.
Specific embodiment
To keep technical solution of the present invention and advantage clearer, below in conjunction with specific embodiment, to skill of the invention Art scheme is clearly and completely described, it is clear that and described embodiments are some of the embodiments of the present invention, rather than all Embodiment.Based on the embodiments of the present invention, those of ordinary skill in the art institute without creative efforts The every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
The preparation of porous silicon-carbon cathode material:
(1) SiO of certain mass is weighed by the mass ratio of the material 1:12Powder and metal Mg powder, are added to ball in ball grinder 1h is ground, is warming up to 650 DEG C in a nitrogen atmosphere with the heating rate of 10 DEG C/min, keeps the temperature and is heat-treated 4h, cooled to room temperature, Generate SiOxThe product is obtained D through broken classification than the mix products for being about 1:1 by (x ≈ 1) and MgO molecular weight50In 3~7 μm SiOx(x ≈ 1) and MgO compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxIt is placed in hydrochloric acid and reacts with MgO compound particles, filter, and It is primary that the acid pickling step is repeated again, is removed MgO impurity and is obtained porous SiOx；By the porous SiO after picklingxIt is placed in deionization In water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum drying 85 DEG C of vacuum drying 2h in case obtain the porous SiO that the porosity of free from admixture no moisture is 50%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 10:1 is configured to uniform conduction by carbon nanotube, conductive black Agent solution；
(4) the porous SiO for obtaining step (2)xIt is added in the conductive agent solution that step (3) obtain, wherein SiOxWith conduction The component ratio of agent is 10:1, stirs 1h under the mixing speed of 800r/min, is uniformly mixed it, is put into 85 in vacuum oven DEG C vacuum drying 2h remove solvent, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 3:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 260 DEG C of completion cladding under an inert atmosphere, be continuously heating to 550 DEG C and complete tentatively Carbonization, then it is warming up to 1100 DEG C of high temperature cabonizations for 24 hours, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material and artificial graphite prepared step (5) is in constituent mass than the ratio for 30%:70% Mixing, low speed ball milling 4h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Wherein, porous SiOxPore-creating mechanism it is as follows: utilize SiO2Pyro-oxidation-reduction with active metal Mg is reacted to make Standby synthesis porous silicon.Magnesium becomes molten state at 648.9 DEG C, and volatile formation magnesium steam works as SiO2: the mass ratio of the material example of Mg When for 1:2, reaction are as follows:
Work as SiO2When excessive, reaction are as follows:
MgO is removed by hydrochloric acid, porous SiO can be preparedx。
Wherein, the porous silicon carbon material preparation flow of the present embodiment is as shown in Figure 1.
The preparation of lithium ion battery:
By porous silicon-carbon cathode material: Super-P:LA133=96:1:3 prepares slurry, is coated on micropore copper foil and is made Silicon-carbon cathode pole piece；
Cut-parts are carried out to silicon-carbon cathode pole piece, pole piece thickness is tested, is button cell to electrode and ginseng using metal lithium sheet Than electrode, electrolyte is 1mol/L LiFP6+ EC/DEC (1:1)+2%VC solution, PP microporous barrier are diaphragm, are being full of argon gas The assembling of glove box progress button cell.
Using the microscopic appearance of porous silicon-carbon cathode material made from scanning electron microscope observation embodiment 1.Test knot Fruit is as shown in Fig. 2, can be seen that the artificial graphite that the material granule that embodiment 1 obtains is divided into bulky grain by scanning electron microscope Grain and short grained porous silicon carbon material particles, the porous silicon carbon material surface pattern uniformity.
First charge-discharge efficiency test is carried out to porous silicon-carbon cathode material made from embodiment 1.Test result such as Fig. 3 institute Show, tested by first charge-discharge efficiency, it is 487.8mAh/g, first charge-discharge effect that the material of embodiment 1 takes off lithium capacity for the first time Rate is 87.86%, shows porous silicon-carbon cathode material of the invention de- lithium capacity with higher and higher first charge-discharge Efficiency.
Cycle performance test is carried out to porous silicon-carbon cathode material made from embodiment 1.Test results are shown in figure 4, real Applying the material of example 1 capacity retention ratio after circulation 500 times is 94.6%, and it is good to show that porous silicon-carbon cathode material of the invention has Good cycle performance.
Cubical expansivity test is carried out to the negative material of porous silicon-carbon made from embodiment 1.As a result the full embedding of embodiment 1 is measured Pole piece cubical expansivity is 19.51%, shows that porous silicon-carbon cathode material cubical expansivity of the invention is lower.
Embodiment 2
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 1.2:12Powder and metal Zn powder, are added in ball grinder Ball milling 1h, is warming up to 650 DEG C in a nitrogen atmosphere with the heating rate of 10 DEG C/min, and heat preservation heat treatment 4h naturally cools to room Temperature generates SiOxWith ZnO molecular weight than the mix products for being about 1:1, which is obtained into D through broken classification50In 3~7 μm SiOxWith ZnO compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxIt is placed in hydrochloric acid and reacts with ZnO compound particles, filter, and It is primary that the acid pickling step is repeated again, is removed ZnO impurity and is obtained porous SiOx；By the porous SiO after picklingxIt is placed in deionization In water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum drying 85 DEG C of vacuum drying 2h in case obtain the porous SiO that the porosity of free from admixture no moisture is 80%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 10:1 is configured to uniform conduction by carbon nanotube, conductive black Agent solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:1, stirs 1h under the mixing speed of 800r/min, is uniformly mixed it, is put into 85 in vacuum oven DEG C vacuum drying 2h remove solvent, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 3:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 260 DEG C of completion cladding under an inert atmosphere, be continuously heating to 550 DEG C and complete tentatively Carbonization, then it is warming up to 1100 DEG C of high temperature cabonizations for 24 hours, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material and artificial graphite prepared step (5) is in constituent mass than the ratio for 30%:70% Mixing, low speed ball milling 4h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 3
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 1:12Powder and metal Mg powder, are added to ball in ball grinder 1h is ground, is warming up to 650 DEG C in a nitrogen atmosphere with the heating rate of 10 DEG C/min, keeps the temperature and is heat-treated 4h, cooled to room temperature, Generate SiOxThe product is obtained D through broken classification than the mix products for being about 1:1 by (x ≈ 1) and MgO molecular weight50In 3~7 μm SiOx(x ≈ 1) and MgO compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxIt is placed in hydrochloric acid and reacts with MgO compound particles, filter, and It is primary that the acid pickling step is repeated again, is removed MgO impurity and is obtained porous SiOx；By the porous SiO after picklingxIt is placed in deionization In water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum drying 85 DEG C of vacuum drying 2h in case obtain the porous SiO that the porosity of free from admixture no moisture is 60%x；
(3) to be in mass ratio that 5:1 is configured to uniform conductive agent for graphene, conductive black using dispersing agent PVP 30 molten Liquid；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 8:1, stirs 1h under the mixing speed of 800r/min, is uniformly mixed it, is put into 85 in vacuum oven DEG C vacuum drying 2h remove solvent, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 3:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 260 DEG C of completion cladding under an inert atmosphere, be continuously heating to 550 DEG C and complete tentatively Carbonization, then it is warming up to 1100 DEG C of high temperature cabonizations for 24 hours, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material and micro crystal graphite prepared step (5) is in constituent mass than the ratio for 30%:70% Mixing, low speed ball milling 4h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 4
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 1.1:12Powder and metal Zn powder, are added in ball grinder Ball milling 1h, is warming up to 650 DEG C in a nitrogen atmosphere with the heating rate of 10 DEG C/min, and heat preservation heat treatment 4h naturally cools to room Temperature generates SiOx and ZnO molecular weight than the mix products for being about 1:1, which is obtained D through broken classification50In 3~7 μm SiOxWith ZnO compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxIt is placed in hydrochloric acid and reacts with ZnO compound particles, filter, and It is primary that the acid pickling step is repeated again, is removed ZnO impurity and is obtained porous SiOx；By the porous SiO after picklingxIt is placed in deionization In water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum drying 85 DEG C of vacuum drying 2h in case obtain the porous SiO that the porosity of free from admixture no moisture is 70%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 10:1 is configured to uniform conduction by carbon nanotube, conductive black Agent solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:1, stirs 1h under the mixing speed of 800r/min, is uniformly mixed it, is put into 85 in vacuum oven DEG C vacuum drying 2h remove solvent, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by asphalt and step (4)xParticle is 2.8:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 260 DEG C of completion cladding under an inert atmosphere, be continuously heating to 550 DEG C and complete tentatively Carbonization, then it is warming up to 1100 DEG C of high temperature cabonizations for 24 hours, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material of step (5) preparation and soft carbon is more mixed than the ratio for 30%:70% in constituent mass It closes, low speed ball milling 4h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 5
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 1:12Powder and metal Mg powder, are added to ball in ball grinder 1h is ground, is warming up to 650 DEG C in a nitrogen atmosphere with the heating rate of 10 DEG C/min, keeps the temperature and is heat-treated 4h, cooled to room temperature, Generate SiOxThe product is obtained D through broken classification than the mix products for being about 1:1 by (x ≈ 1) and MgO molecular weight50In 3~7 μm SiOx(x ≈ 1) and MgO compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxIt is placed in hydrochloric acid and reacts with MgO compound particles, filter, and It is primary that the acid pickling step is repeated again, is removed MgO impurity and is obtained porous SiOx；By the porous SiO after picklingxIt is placed in deionization In water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum drying 85 DEG C of vacuum drying 2h in case obtain the porous SiO that the porosity of free from admixture no moisture is 40%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 10:1 is configured to uniform conductive agent by graphene, conductive black Solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:1, stirs 1h under the mixing speed of 800r/min, is uniformly mixed it, is put into 85 in vacuum oven DEG C vacuum drying 2h remove solvent, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 3:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 260 DEG C of completion cladding under an inert atmosphere, be continuously heating to 550 DEG C and complete tentatively Carbonization, then it is warming up to 1100 DEG C of high temperature cabonizations for 24 hours, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material of step (5) preparation and carbonaceous mesophase spherules are pressed into constituent mass than for 40%:60%'s Ratio mixing, low speed ball milling 4h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 6
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 1:12Powder and metal Mg powder, are added to ball in ball grinder 1h is ground, is warming up to 1000 DEG C under an argon atmosphere with the heating rate of 10 DEG C/min, heat preservation heat treatment 10h naturally cools to room Temperature generates SiOxThe product is obtained D through broken classification than the mix products for being about 1:1 by (x ≈ 1) and MgO molecular weight50In 3 ~7 μm of SiOx(x ≈ 1) and MgO compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxIt is placed in hydrochloric acid and reacts with MgO compound particles, filter, and It is primary that the acid pickling step is repeated again, is removed MgO impurity and is obtained porous SiOx；By the porous SiO after picklingxIt is placed in deionization In water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum drying 85 DEG C of vacuum drying 2h in case obtain the porous SiO that the porosity of free from admixture no moisture is 30%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 5:5:1 is configured to by carbon nanotube, graphene, conductive black Even conductive agent solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:2, stirs 3h under the mixing speed of 1500r/min, is uniformly mixed it, is put into vacuum oven 150 DEG C of vacuum drying 1h remove solvent, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 5:1 in mass ratio Ratio mixing, ball milling merges 1h, is heated to 270 DEG C of completion cladding under an inert atmosphere, be continuously heating to 600 DEG C and complete tentatively Carbonization, then 1000 DEG C of high temperature cabonization 16h are warming up to, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material of step (5) preparation and carbonaceous mesophase spherules are pressed into constituent mass than for 20%:80%'s Ratio mixing, low speed ball milling 2h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 7
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 1:12Powder and metal iron powder end, are added to ball in ball grinder 1h is ground, is warming up to 1000 DEG C under an argon atmosphere with the heating rate of 10 DEG C/min, heat preservation heat treatment 20h naturally cools to room Temperature generates SiOx(x ≈ 1) and Fe2O3The product is obtained D through broken classification than the mix products for being about 1:1 by molecular weight50It is in 3~7 μm of SiOx(x ≈ 1) and Fe2O3Compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxAnd Fe2O3Compound particles, which are placed in hydrochloric acid, to react, filtering, And it is primary to repeat the acid pickling step again, removes Fe2O3Impurity obtains porous SiOx；By the porous SiO after picklingxIt is placed in In ionized water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum 85 DEG C of vacuum drying 2h in drying box obtain the porous SiO that the porosity of free from admixture no moisture is 20%x；
(3) carbon nanotube, graphene, conductive black are configured in mass ratio for 10:10:1 using dispersing agent PVP 30 Uniform conduction agent solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:0.5, stirs 3h under the mixing speed of 500r/min, is uniformly mixed it, is put into vacuum oven 150 DEG C of vacuum drying 1h remove solvent, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 4:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 270 DEG C of completion cladding under an inert atmosphere, be continuously heating to 500 DEG C and complete tentatively Carbonization, then 1000 DEG C of high temperature cabonization 10h are warming up to, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material of step (5) preparation and carbonaceous mesophase spherules are pressed into constituent mass than for 10%:90%'s Ratio mixing, low speed ball milling 2h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 8
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 1:12Powder and metal iron powder end, are added to ball in ball grinder 1h is ground, is warming up to 650 DEG C under helium atmosphere with the heating rate of 10 DEG C/min, keeps the temperature and is heat-treated 8h, cooled to room temperature, Generate SiOx(x ≈ 1) and Fe2O3The product is obtained D through broken classification than the mix products for being about 1:1 by molecular weight50In 3~ 7 μm of SiOx(x ≈ 1) and Fe2O3Compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxAnd Fe2O3Compound particles, which are placed in hydrochloric acid, to react, filtering, And it is primary to repeat the acid pickling step again, removes Fe2O3Impurity obtains porous SiOx；By the porous SiO after picklingxIt is placed in In ionized water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum 85 DEG C of vacuum drying 2h in drying box obtain the porous SiO that the porosity of free from admixture no moisture is 45%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 15:1 is configured to uniform conductive agent by graphene, conductive black Solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:1.5, stirs 3h under the mixing speed of 500r/min, is uniformly mixed it, is put into vacuum oven 60 DEG C of vacuum drying 1h remove solvent, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 4:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 260 DEG C of completion cladding under an inert atmosphere, be continuously heating to 550 DEG C and complete tentatively Carbonization, then 1100 DEG C of high temperature cabonization 15h are warming up to, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material of step (5) preparation and carbonaceous mesophase spherules are pressed into constituent mass than for 5%:95%'s Ratio mixing, low speed ball milling 4h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 9
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 1:12Powder and metal Mg powder, are added to ball in ball grinder 1h is ground, is warming up to 750 DEG C under helium atmosphere with the heating rate of 10 DEG C/min, heat preservation heat treatment 12h naturally cools to room Temperature generates SiOxThe product is obtained D through broken classification than the mix products for being about 1:1 by (x ≈ 1) and MgO molecular weight50In 3 ~7 μm of SiOx(x ≈ 1) and MgO compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxIt is placed in hydrochloric acid and reacts with MgO compound particles, filter, and It is primary that the acid pickling step is repeated again, is removed MgO impurity and is obtained porous SiOx；By the porous SiO after picklingxIt is placed in deionization In water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum drying 85 DEG C of vacuum drying 2h in case obtain the porous SiO that the porosity of free from admixture no moisture is 55%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 12:1 is configured to uniform conduction by carbon nanotube, conductive black Agent solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:2, stirs 0.5h under the mixing speed of 1000r/min, is uniformly mixed it, is put into vacuum oven In 80 DEG C of vacuum drying 2.5h remove solvents, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 3:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 260 DEG C of completion cladding under an inert atmosphere, be continuously heating to 550 DEG C and complete tentatively Carbonization, then 1100 DEG C of high temperature cabonization 15h are warming up to, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material of step (5) preparation and carbonaceous mesophase spherules are pressed into constituent mass than for 15%:85%'s Ratio mixing, low speed ball milling 4h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 10
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 1:12Powder and metal Mg powder, are added to ball in ball grinder 1h is ground, is warming up to 850 DEG C under helium atmosphere with the heating rate of 10 DEG C/min, heat preservation heat treatment 16h naturally cools to room Temperature generates SiOxThe product is obtained D through broken classification than the mix products for being about 1:1 by (x ≈ 1) and MgO molecular weight50In 3 ~7 μm of SiOx(x ≈ 1) and MgO compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxIt is placed in hydrochloric acid and reacts with MgO compound particles, filter, and It is primary that the acid pickling step is repeated again, is removed MgO impurity and is obtained porous SiOx；By the porous SiO after picklingxIt is placed in deionization In water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum drying 85 DEG C of vacuum drying 2h in case obtain the porous SiO that the porosity of free from admixture no moisture is 65%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 18:1 is configured to uniform conductive agent by graphene, conductive black Solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:2, stirs 0.5h under the mixing speed of 1000r/min, is uniformly mixed it, is put into vacuum oven In 80 DEG C of vacuum drying 2.5h remove solvents, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 3:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 265 DEG C of completion cladding under an inert atmosphere, be continuously heating to 580 DEG C and complete tentatively Carbonization, then 1050 DEG C of high temperature cabonization 18h are warming up to, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material of step (5) preparation and carbonaceous mesophase spherules are pressed into constituent mass than for 20%:80%'s Ratio mixing, low speed ball milling 4h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 11
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 1:12Powder and metal Zn powder, are added to ball in ball grinder 1h is ground, is warming up to 950 DEG C in a nitrogen atmosphere with the heating rate of 10 DEG C/min, heat preservation heat treatment 18h naturally cools to room Temperature generates SiOxThe product is obtained D through broken classification than the mix products for being about 1:1 by (x ≈ 1) and ZnO molecular weight50In 3 ~7 μm of SiOx(x ≈ 1) and ZnO compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxIt is placed in hydrochloric acid and reacts with ZnO compound particles, filter, and It is primary that the acid pickling step is repeated again, is removed ZnO impurity and is obtained porous SiOx；By the porous SiO after picklingxIt is placed in deionization In water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum drying 85 DEG C of vacuum drying 2h in case obtain the porous SiO that the porosity of free from admixture no moisture is 75%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 20:1 is configured to uniform conductive agent by graphene, conductive black Solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:1, stirs 0.5h under the mixing speed of 1000r/min, is uniformly mixed it, is put into vacuum oven In 100 DEG C of vacuum drying 2.5h remove solvents, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 1:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 260 DEG C of completion cladding under an inert atmosphere, be continuously heating to 600 DEG C and complete tentatively Carbonization, then 1100 DEG C of high temperature cabonization 20h are warming up to, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material of step (5) preparation and carbonaceous mesophase spherules are pressed into constituent mass than for 40%:60%'s Ratio mixing, low speed ball milling 2h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 12
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 1:12Powder and metal Zn powder, are added to ball in ball grinder 1h is ground, is warming up to 1000 DEG C in a nitrogen atmosphere with the heating rate of 10 DEG C/min, heat preservation heat treatment 20h naturally cools to room Temperature generates SiOxThe product is obtained D through broken classification than the mix products for being about 1:1 by (x ≈ 1) and ZnO molecular weight50In 3 ~7 μm of SiOx(x ≈ 1) and ZnO compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxIt is placed in hydrochloric acid and reacts with ZnO compound particles, filter, and It is primary that the acid pickling step is repeated again, is removed ZnO impurity and is obtained porous SiOx；By the porous SiO after picklingxIt is placed in deionization In water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum drying 85 DEG C of vacuum drying 2h in case obtain the porous SiO that the porosity of free from admixture no moisture is 40%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 10:1 is configured to uniform conduction by carbon nanotube, conductive black Agent solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:1.5, stirs 2.5h under the mixing speed of 1000r/min, is uniformly mixed it, is put into vacuum drying 120 DEG C of vacuum drying 3h remove solvent in case, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 1:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 260 DEG C of completion cladding under an inert atmosphere, be continuously heating to 500 DEG C and complete tentatively Carbonization, then 1000 DEG C of high temperature cabonization 22h are warming up to, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material of step (5) preparation and carbonaceous mesophase spherules are pressed into constituent mass than for 50%:50%'s Ratio mixing, low speed ball milling 4h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 13
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 0.8:12Powder and metal Zn powder, are added in ball grinder Ball milling 2.5h is warming up to 1000 DEG C, heat preservation heat treatment 22h in a nitrogen atmosphere with the heating rate of 10 DEG C/min, natural cooling To room temperature, SiO is generatedxThe product is obtained D through broken classification than the mix products for being about 1:1 by (x ≈ 1) and ZnO molecular weight50 In 3~7 μm of SiOx(x ≈ 1) and ZnO compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxIt is placed in hydrochloric acid and reacts with ZnO compound particles, filter, and It is primary that the acid pickling step is repeated again, is removed ZnO impurity and is obtained porous SiOx；By the porous SiO after picklingxIt is placed in deionization In water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum drying 85 DEG C of vacuum drying 2h in case obtain the porous SiO that the porosity of free from admixture no moisture is 50%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 10:5:1 is configured to by carbon nanotube, graphene, conductive black Even conductive agent solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:2, stirs 2.5h under the mixing speed of 1000r/min, is uniformly mixed it, is put into vacuum oven In 130 DEG C of vacuum drying 2h remove solvents, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 1:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 260 DEG C of completion cladding under an inert atmosphere, be continuously heating to 550 DEG C and complete tentatively Carbonization, then it is warming up to 1100 DEG C of high temperature cabonizations for 24 hours, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material of step (5) preparation and carbonaceous mesophase spherules are pressed into constituent mass than for 50%:50%'s Ratio mixing, low speed ball milling 4h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 14
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 1.2:12Powder and metal Zn powder, are added in ball grinder Ball milling 3h is warming up to 1000 DEG C in a nitrogen atmosphere with the heating rate of 10 DEG C/min, and heat preservation heat treatment for 24 hours, naturally cools to Room temperature generates SiOxThe product is obtained D through broken classification than the mix products for being about 1:1 by (x ≈ 1) and ZnO molecular weight50Place In 3~7 μm of SiOx(x ≈ 1) and ZnO compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxIt is placed in hydrochloric acid and reacts with ZnO compound particles, filter, and It is primary that the acid pickling step is repeated again, is removed ZnO impurity and is obtained porous SiOx；By the porous SiO after picklingxIt is placed in deionization In water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum drying 85 DEG C of vacuum drying 2h in case obtain the porous SiO that the porosity of free from admixture no moisture is 60%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 5:3:1 is configured to by carbon nanotube, graphene, conductive black Even conductive agent solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:1, stirs 3h under the mixing speed of 1000r/min, is uniformly mixed it, is put into vacuum oven 130 DEG C of vacuum drying 2h remove solvent, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 1:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 260 DEG C of completion cladding under an inert atmosphere, be continuously heating to 550 DEG C and complete tentatively Carbonization, then it is warming up to 1100 DEG C of high temperature cabonizations for 24 hours, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material of step (5) preparation and carbonaceous mesophase spherules are pressed into constituent mass than for 40%:60%'s Ratio mixing, low speed ball milling 4h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 15
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 0.9:12Powder and metal iron powder end, are added in ball grinder Ball milling 4h is warming up to 1000 DEG C in a nitrogen atmosphere with the heating rate of 10 DEG C/min, and heat preservation heat treatment for 24 hours, naturally cools to Room temperature generates SiOx(x ≈ 1) and Fe2O3The product is obtained D through broken classification than the mix products for being about 1:1 by molecular weight50Place In 3~7 μm of SiOx(x ≈ 1) and Fe2O3Compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxAnd Fe2O3Compound particles, which are placed in hydrochloric acid, to react, filtering, And it is primary to repeat the acid pickling step again, removes Fe2O3Impurity obtains porous SiOx；By the porous SiO after picklingxIt is placed in In ionized water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum 85 DEG C of vacuum drying 2h in drying box obtain the porous SiO that the porosity of free from admixture no moisture is 70%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 5:10:1 is configured to by carbon nanotube, graphene, conductive black Even conductive agent solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:1, stirs 2.5h under the mixing speed of 1000r/min, is uniformly mixed it, is put into vacuum oven In 140 DEG C of vacuum drying 2h remove solvents, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 1:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 260 DEG C of completion cladding under an inert atmosphere, be continuously heating to 550 DEG C and complete tentatively Carbonization, then it is warming up to 1100 DEG C of high temperature cabonizations for 24 hours, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material of step (5) preparation and carbonaceous mesophase spherules are pressed into constituent mass than for 40%:60%'s Ratio mixing, low speed ball milling 4h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 16
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 1.1:12Powder and metal iron powder end, are added in ball grinder Ball milling 4h, is warming up to 1000 DEG C in a nitrogen atmosphere with the heating rate of 10 DEG C/min, and heat preservation heat treatment 10h is naturally cooled to Room temperature generates SiOx(x ≈ 1) and Fe2O3The product is obtained D through broken classification than the mix products for being about 1:1 by molecular weight50Place In 3~7 μm of SiOx(x ≈ 1) and Fe2O3Compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxAnd Fe2O3Compound particles, which are placed in hydrochloric acid, to react, filtering, And it is primary to repeat the acid pickling step again, removes Fe2O3Impurity obtains porous SiOx；By the porous SiO after picklingxIt is placed in In ionized water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum 85 DEG C of vacuum drying 2h in drying box obtain the porous SiO that the porosity of free from admixture no moisture is 80%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 10:8:1 is configured to by carbon nanotube, graphene, conductive black Even conductive agent solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:1, stirs 2.5h under the mixing speed of 1000r/min, is uniformly mixed it, is put into vacuum oven In 150 DEG C of vacuum drying 1h remove solvents, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 1:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 260 DEG C of completion cladding under an inert atmosphere, be continuously heating to 550 DEG C and complete tentatively Carbonization, then 1100 DEG C of high temperature cabonization 20h are warming up to, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material of step (5) preparation and carbonaceous mesophase spherules are pressed into constituent mass than for 30%:70%'s Ratio mixing, low speed ball milling 4h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 17
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 1.1:12Powder and metal Mg powder, are added in ball grinder Ball milling 4h is warming up to 1000 DEG C in a nitrogen atmosphere with the heating rate of 10 DEG C/min, and heat preservation heat treatment for 24 hours, naturally cools to Room temperature generates SiOxThe product is obtained D through broken classification than the mix products for being about 1:1 by (x ≈ 1) and MgO molecular weight50Place In 3~7 μm of SiOx(x ≈ 1) and MgO compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxIt is placed in hydrochloric acid and reacts with MgO compound particles, filter, and It is primary that the acid pickling step is repeated again, is removed MgO impurity and is obtained porous SiOx；By the porous SiO after picklingxIt is placed in deionization In water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum drying 85 DEG C of vacuum drying 2h in case obtain the porous SiO that the porosity of free from admixture no moisture is 60%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 5:5:1 is configured to by carbon nanotube, graphene, conductive black Even conductive agent solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:1, stirs 2.5h under the mixing speed of 1000r/min, is uniformly mixed it, is put into vacuum oven In 150 DEG C of vacuum drying 1h remove solvents, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 1:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 260 DEG C of completion cladding under an inert atmosphere, be continuously heating to 600 DEG C and complete tentatively Carbonization, then it is warming up to 1000 DEG C of high temperature cabonizations for 24 hours, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material of step (5) preparation and carbonaceous mesophase spherules are pressed into constituent mass than for 30%:70%'s Ratio mixing, low speed ball milling 4h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 18
The preparation of the present embodiment porous silicon-carbon cathode material unlike the first embodiment:
(1) SiO of certain mass is weighed by the mass ratio of the material 1.2:12Powder and metal Mg powder, are added in ball grinder Ball milling 4h is warming up to 1000 DEG C in a nitrogen atmosphere with the heating rate of 10 DEG C/min, and heat preservation heat treatment for 24 hours, naturally cools to Room temperature generates SiOxThe product is obtained D through broken classification than the mix products for being about 1:1 by (x ≈ 1) and MgO molecular weight50Place In 3~7 μm of SiOx(x ≈ 1) and MgO compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxIt is placed in hydrochloric acid and reacts with MgO compound particles, filter, and It is primary that the acid pickling step is repeated again, is removed MgO impurity and is obtained porous SiOx；By the porous SiO after picklingxIt is placed in deionization In water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum drying 85 DEG C of vacuum drying 2h in case obtain the porous SiO that the porosity of free from admixture no moisture is 70%x；
It (3) the use of dispersing agent PVP 30 is in mass ratio that 8:5:1 is configured to by carbon nanotube, graphene, conductive black Even conductive agent solution；
(4) the porous SiO for obtaining step (2)xIt is added in conduction agent solution made from step (3), wherein SiOxWith conduction The component ratio of agent is 10:1, stirs 2.5h under the mixing speed of 1000r/min, is uniformly mixed it, is put into vacuum oven In 150 DEG C of vacuum drying 1h remove solvents, obtain the porous SiO of surface coated with conductive agentxParticle；
(5) by the porous SiO of coated with conductive agent prepared by coal tar asphalt and step (4)xParticle is 1:1 in mass ratio Ratio mixing, ball milling merges 3h, is heated to 260 DEG C of completion cladding under an inert atmosphere, be continuously heating to 600 DEG C and complete tentatively Carbonization, then it is warming up to 1000 DEG C of high temperature cabonizations for 24 hours, obtain the porous silicon carbon material of three-decker；
(6) the porous silicon carbon material of step (5) preparation and carbonaceous mesophase spherules are pressed into constituent mass than for 40%:60%'s Ratio mixing, low speed ball milling 4h is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
Remaining is with embodiment 1, and which is not described herein again.
Comparative example 1
Difference with embodiment is that the preparation of this comparative example silicon-carbon cathode material does not carry out step (1) and step (2), adopts With the SiO of non-porous structurexReplace porous SiOx.Its it is specific the preparation method is as follows:
It (1) the use of dispersing agent PVP 30 is in mass ratio that 10:1 is configured to solution by carbon nanotube, conductive black；
(2) by non-porous SiOxIt is added in the hybrid conductive agent solution, wherein SiOxComponent ratio with conductive agent is 10:1, with The mixing speed of 800r/min stirs 1h, is uniformly mixed it, is put into 85 DEG C of vacuum drying 2h in vacuum oven and removes solvent, Obtain the non-porous SiO of surface coated with conductive agentxParticle；
(3) by the SiO of coal tar asphalt and coated with conductive agentxParticle is the ratio mixing of 3:1, ball milling fusion in mass ratio 3h is heated to 260 DEG C of completion claddings under an inert atmosphere, is heated to 550 DEG C and completes preliminary carbonization, is again heated to 1100 DEG C of high temperature Carbonization for 24 hours, obtains the silicon carbon material of three-decker；
(4) by the silicon carbon material and artificial graphite in constituent mass than being mixed for the ratio of 30%:70%, in ball grinder Low speed ball milling 4h is uniformly mixed it to get the silicon-carbon cathode material of comparative example 1 is arrived.
Comparative example 2
Difference with embodiment is the preparation of this comparative example silicon-carbon cathode material without step (3) and step (4) The encapsulation steps of conductive agent.Its it is specific the preparation method is as follows:
(1) SiO of certain mass is weighed by the mass ratio of the material 1:12Powder and metal Mg powder, are added to ball in ball grinder 1h is ground, is warming up to 650 DEG C in a nitrogen atmosphere with the heating rate of 10 DEG C/min, keeps the temperature and is heat-treated 4h, cooled to room temperature, Generate SiOxThe product is handled to obtain D by (x ≈ 1) and MgO molecular weight than the mix products for being about 1:1 through broken classification50It is in 3~7 μm of SiOx(x ≈ 1) and MgO compound particles；
(2) compound concentration is the hydrochloric acid of 1mol/L, by SiOxIt is placed in hydrochloric acid and reacts with MgO compound particles, filter, and It is primary that the acid pickling step is repeated again, is removed MgO impurity and is obtained porous SiOx；By the porous SiO after picklingxIt is placed in deionization In water, it is cleaned by ultrasonic 10min, filtering, and repeat the step 3~5 time again；By the porous SiO after washingxIt is put into vacuum drying 85 DEG C of vacuum drying 2h, obtain the porous SiO of free from admixture no moisture in casex；
(3) by coal tar asphalt and porous SiOxParticle is the ratio mixing of 3:1 in mass ratio, and ball milling merges 3h, lazy Property atmosphere under be heated to 260 DEG C of completions cladding, be heated to 550 DEG C and complete preliminary carbonization, be again heated to 1100 DEG C of high temperature cabonizations For 24 hours, the porous silicon carbon material of core-shell structure is obtained；
(4) by porous silicon carbon material and artificial graphite in constituent mass than being mixed for the ratio of 30%:70%, in ball grinder Middle low speed ball milling 4h is uniformly mixed it to get the porous silicon-carbon cathode material is arrived.
Electrochemical property test is carried out to silicon-carbon cathode material made from embodiment 1~18 and comparative example 1~2 respectively, is surveyed Test result is shown in Table 1.
The electrochemical property test result of silicon-carbon cathode material made from 1 embodiment and comparative example of table
It can be obtained by the test result of table 1:
1) initial reversible specific capacity >=487.8mAh/g of the invention, first charge discharge efficiency >=87.86% show of the invention more Hole silicon-carbon cathode material de- lithium capacity with higher and higher first charge-discharge efficiency.Since internal porous structure is reserved The space of volume expansion, reduces material because of the stress that volume expansion generates and ruptures dusting, and then efficiently avoid material Electrical contact, while SiO are lost between materialxCarbon nano tube/graphene+Super the P of surface covering improves the electric conductivity of material, Greatly reduce the capacitance loss of the generation because ion transmission is obstructed.
Material surface cladding amorphous carbon formed during first charge-discharge electrolyte consumed by SEI membrane process and Li+It is fewer than silicon materials consumption, and the SEI film formed is more uniformly stablized, it can be to avoid internal SiOxWith connecing for electrolyte Touch reaction.The structure and the carbon nano tube/graphene+Super P of surface covering limit the SiO of kernelxIn embedding lithium Expansion and the generation of crackle avoid electrolyte from entering crackle and generate cenotype, to reduce to electrolyte and Li+Consumption.
2) cubical expansivity≤19.51% of porous silicon-carbon cathode pole piece of the invention, when expiring embedding lithium well below pure Si Cubical expansivity 300%, lower than the SiO for using non-porous structurex37.25%, do not carry out conductive agent cladding slightly below 22.66%.Analysis reason has at following 4 points:
(a)SiOxAlthough lower as the purer Si capacity of kernel, volume change is also reduced accordingly；
(b) SiO of porous structurexCertain space has been reserved in volume expansion when kernel is embedding lithium, can satisfy substantially Volume expansion when embedding lithium；
(c) amorphous carbon of the conductive agent network and outer layer that coat limits SiOxKernel is to external expansion；
(d) porous silicon carbon material and graphite material are mixed with porous silicon-carbon cathode material, further reduced cathode Volume expansion.
3) porous silicon-carbon cathode pole piece of the invention capacity retention ratio >=94.6% after circulation 500 times, shows the present invention Porous silicon-carbon cathode material have good cycle performance.
The reason of causing the capacitance loss of silicon-carbon cathode causes the broken of material mainly include the following types: volume expansion is shunk Split, dusting, lose electrical contact after ion transmission be obstructed caused by irreversible capacity；SEI film caused by volume expansion-contraction is repeatedly Rupture-generation, it is continuous to consume lithium ion and electrolyte；HF after the rupture of SEI film in electrolyte and electrolyte etc. and silicon-carbon are negative Side reaction occurs for pole, consumes Si, Li+And electrolyte, the product that side reaction generates further deteriorate battery performance.The present invention adopts With three layers of core-shell type compound structure design, effectively inhibit above situation.
During multiple charge and discharge cycles, because of the porous SiO of materialxStructure exists, and provides and expands for material Space, simultaneously as the carbon nano tube/graphene+Super P network and amorphous carbon on surface, while enhancing electric conductivity It inhibits material to be in electrical contact the transmission of ion caused by variation in the breaking and Dusting of cyclic process stress to be obstructed, reduces and be circulated throughout Irreversible capacity caused by being obstructed in journey because of ion transmission.
Since surface has coated amorphous carbon, the surface in cyclic process for the first time in amorphous carbon forms good SEI film, because porous and cladding structure design avoids material surface SEI caused by huge volume change in removal lithium embedded Continuous rupture-regeneration process of film, also avoids because of SiOxExposure in the electrolytic solution and the micro-crack of particle and electrolyte it is anti- Cenotype should be formed, electrolyte caused by reducing in cyclic process and Li+A large amount of consumption caused by capacitance loss.
The silicon-carbon cathode of three-decker design is by solving volume change, intergranular electrical contact, SiOxWith electrolysis The problem of reaction of liquid, reduce ion transmission be obstructed caused capacitance loss, SEI film constantly rupture generation caused by capacity damage Mistake and SiOxConsumption electrolyte and Li are reacted with electrolyte+Caused capacitance loss, to improve the cyclicity of material Energy.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula is changed and is modified.Therefore, the invention is not limited to above-mentioned specific embodiment, all those skilled in the art exist Made any conspicuous improvement, replacement or modification all belong to the scope of protection of the present invention on the basis of the present invention.This Outside, although using some specific terms in this specification, these terms are merely for convenience of description, not to the present invention Constitute any restrictions.

Claims (20)

1. a kind of porous silicon-carbon cathode material, it is characterised in that: including porous silicon carbon material and graphite material；The porous silicon-carbon Material is core-shell structure, including kernel and is successively coated on the middle layer and outermost layer of kernel, and the kernel is noncrystalline, porous Silicon oxygen material SiOx, wherein 0 x≤2 <, the middle layer are reticulated conductive agent clad, and the outermost layer is amorphous carbon packet Coating.
2. porous silicon-carbon cathode material according to claim 1, it is characterised in that: the porous silicon oxygen material SiOxHole Gap rate is 20~80%.
3. porous silicon-carbon cathode material according to claim 1, it is characterised in that: the porous silicon oxygen material SiOxIn It is worth partial size D50It is 3~7 μm.
4. porous silicon-carbon cathode material according to claim 1, it is characterised in that: the conductive agent clad with a thickness of 10~100nm.
5. porous silicon-carbon cathode material according to claim 1, it is characterised in that: the conductive agent include conductive agent A and Conductive agent B, the conductive agent A are at least one of carbon nanotube, graphene, and the conductive agent B is conductive black.
6. porous silicon-carbon cathode material according to claim 1, it is characterised in that: the thickness of the amorphous carbon coating layer It is 0.5~2 μm.
7. porous silicon-carbon cathode material according to claim 1, it is characterised in that: the amorphous carbon be asphalt, One or more of coal tar asphalt is formed after being carbonized.
8. porous silicon-carbon cathode material according to claim 1, it is characterised in that: the porous silicon carbon material and the stone The mass ratio of ink material is 5~50%:50~95%.
9. porous silicon-carbon cathode material according to claim 1, it is characterised in that: the porous silicon oxygen material SiOx, it is described The mass ratio of conductive agent and the amorphous carbon is 20~50%:5~20%:30~75%.
10. porous silicon-carbon cathode material according to claim 1, it is characterised in that: the graphite material be natural graphite, At least one of artificial graphite, micro crystal graphite, carbonaceous mesophase spherules, soft carbon.
11. a kind of preparation method of porous silicon-carbon cathode material, which comprises the following steps:
Step 1), by Si oxide SiOxIn the mass ratio of the material be (0.5~2) with active metal powder: 1 ratio mixes, in ball 1~4h of ball milling is uniformly mixed it in grinding jar, under an inert atmosphere 650~1000 DEG C of heat treatments 4~for 24 hours, is classified through broken To D50For 3~7 μm of Si oxide SiOxAnd metal oxide composite, wherein 0 x≤2 <；
Step 2) carries out pickling to material prepared by step 1) using hydrochloric acid, removes metal oxide, further washing, drying Obtain porous SiOxMaterial；
Conductive agent A and conductive agent B using dispersing agent are (1~20) by step 3) in mass ratio: 1 is configured to uniform conductive agent Solution, wherein conductive agent A is at least one of carbon nanotube, graphene, and conductive agent B is conductive black；
Step 4), the porous SiO for preparing step 2)xMaterial is added in the conductive agent solution of step 3) preparation, porous SiOxMaterial Molar ratio with conductive agent is 10:(0.5~2), 0.5~3h is stirred under the mixing speed of 500~1500r/min, keeps it mixed It closes uniformly, vacuum drying removes solvent, obtains the porous SiO of surface coated with conductive agentxParticle；
Step 5), the coated with conductive agent for preparing pitch and step 4) porous SiOxParticle is (1~5) in mass ratio: 1 ratio Example mixing, ball milling merge 1~3h, are heated to 260~270 DEG C of completion claddings under an inert atmosphere, are continuously heating to 500~600 DEG C preliminary carbonization is completed, then be warming up to 1000~1100 DEG C of high temperature cabonizations 8~for 24 hours, obtains the porous silicon-carbon of three-layer nuclear shell structure Material；
Step 6), by step 5) preparation porous silicon carbon material and graphite material be in mass ratio 5~50%:50~95% ratio Example mixing, 1~4h of ball milling is uniformly mixed it to get porous silicon-carbon cathode material is arrived in ball grinder.
12. the preparation method of porous silicon-carbon cathode material according to claim 11, it is characterised in that: in step 1), institute Stating active metal powder is one or more of magnesium, zinc, iron.
13. the preparation method of porous silicon-carbon cathode material according to claim 11, it is characterised in that: in step 1), institute State Si oxide SiOxThe mass ratio of the material with active metal powder is (0.8~1.2): 1.
14. the preparation method of porous silicon-carbon cathode material according to claim 11, it is characterised in that: step 1) and step 5) in, the inert atmosphere is one of nitrogen, argon gas, helium.
15. the preparation method of porous silicon-carbon cathode material according to claim 11, it is characterised in that: in step 2), institute State porous SiOxThe porosity of material is 20~80%.
16. the preparation method of porous silicon-carbon cathode material according to claim 11, it is characterised in that: in step 3), institute Stating dispersing agent is polyvinylpyrrolidone.
17. the preparation method of porous silicon-carbon cathode material according to claim 11, it is characterised in that: in step 4), institute Stating vacuum drying temperature is 60~150 DEG C, and drying time is 1~3h.
18. the preparation method of porous silicon-carbon cathode material according to claim 11, it is characterised in that: in step 5), institute Stating pitch is one or more of asphalt, coal tar asphalt.
19. the preparation method of porous silicon-carbon cathode material according to claim 11, it is characterised in that: in step 6), institute Stating graphite material is at least one of natural graphite, artificial graphite, micro crystal graphite, carbonaceous mesophase spherules, soft carbon.
20. a kind of lithium ion battery, it is characterised in that: including the described in any item porous silicon-carbon cathode materials of claim 1~10 Material.
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Publication number Priority date Publication date Assignee Title
CN109920989A (en) * 2019-03-01 2019-06-21 沈阳国科金能科技有限公司 A kind of preparation method of three layers of carbon coating composite lithium iron phosphate cathode material
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103022446A (en) * 2012-12-19 2013-04-03 深圳市贝特瑞新能源材料股份有限公司 Silicon oxide/carbon cathode material of lithium ion battery and preparation method of material
CN103165862A (en) * 2013-03-22 2013-06-19 浙江瓦力新能源科技有限公司 High-performance negative material of lithium ion cell and preparation method of material
CN103346293A (en) * 2013-06-28 2013-10-09 中国科学院宁波材料技术与工程研究所 Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery
CN104577045A (en) * 2014-12-20 2015-04-29 江西正拓新能源科技股份有限公司 Silicon-carbon composite material of lithium ion battery and preparation method of silicon-carbon composite material
CN104617276A (en) * 2015-02-10 2015-05-13 南开大学 Lithium ion secondary battery porous silicon/carbon composite negative electrode material and preparation method thereof
CN106410158A (en) * 2016-11-07 2017-02-15 中国科学院化学研究所 Graphene modified silicon monoxide and carbon composite microsphere, and preparation method and application thereof
JP2017212236A (en) * 2017-09-11 2017-11-30 学校法人慶應義塾 Sintered body
CN107819105A (en) * 2017-10-17 2018-03-20 合肥国轩高科动力能源有限公司 A kind of preparation method of silicon-carbon cathode pole piece

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103022446A (en) * 2012-12-19 2013-04-03 深圳市贝特瑞新能源材料股份有限公司 Silicon oxide/carbon cathode material of lithium ion battery and preparation method of material
CN103165862A (en) * 2013-03-22 2013-06-19 浙江瓦力新能源科技有限公司 High-performance negative material of lithium ion cell and preparation method of material
CN103346293A (en) * 2013-06-28 2013-10-09 中国科学院宁波材料技术与工程研究所 Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery
CN104577045A (en) * 2014-12-20 2015-04-29 江西正拓新能源科技股份有限公司 Silicon-carbon composite material of lithium ion battery and preparation method of silicon-carbon composite material
CN104617276A (en) * 2015-02-10 2015-05-13 南开大学 Lithium ion secondary battery porous silicon/carbon composite negative electrode material and preparation method thereof
CN106410158A (en) * 2016-11-07 2017-02-15 中国科学院化学研究所 Graphene modified silicon monoxide and carbon composite microsphere, and preparation method and application thereof
JP2017212236A (en) * 2017-09-11 2017-11-30 学校法人慶應義塾 Sintered body
CN107819105A (en) * 2017-10-17 2018-03-20 合肥国轩高科动力能源有限公司 A kind of preparation method of silicon-carbon cathode pole piece

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109920989A (en) * 2019-03-01 2019-06-21 沈阳国科金能科技有限公司 A kind of preparation method of three layers of carbon coating composite lithium iron phosphate cathode material
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CN110364700B (en) * 2019-05-31 2021-09-03 南方科技大学 Silica composite material, preparation method thereof and lithium ion battery
CN110364700A (en) * 2019-05-31 2019-10-22 南方科技大学 Silicon O compoiste material and preparation method thereof and lithium ion battery
CN111082005A (en) * 2019-12-06 2020-04-28 欣旺达电动汽车电池有限公司 Negative electrode material, composite material and preparation method thereof
CN112952054B (en) * 2019-12-11 2023-05-30 新疆硅基新材料创新中心有限公司 Silicon-based anode material, preparation method thereof, anode and lithium ion battery
CN112952054A (en) * 2019-12-11 2021-06-11 新疆硅基新材料创新中心有限公司 Silicon-based negative electrode material, preparation method, negative electrode and lithium ion battery
CN111653738A (en) * 2020-04-20 2020-09-11 万向一二三股份公司 Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof
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