CN108470891A - The method for preparing silicon-carbon cathode material based on micron silica - Google Patents

The method for preparing silicon-carbon cathode material based on micron silica Download PDF

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CN108470891A
CN108470891A CN201810219122.8A CN201810219122A CN108470891A CN 108470891 A CN108470891 A CN 108470891A CN 201810219122 A CN201810219122 A CN 201810219122A CN 108470891 A CN108470891 A CN 108470891A
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cathode material
material based
carbon cathode
preparing silicon
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CN108470891B (en
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吴振国
吴晨
郭孝东
向伟
钟本和
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Nanchong Central Amperex Technology Ltd
Sichuan University
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Nanchong Central Amperex Technology Ltd
Sichuan University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

Based on the method that micron silica prepares silicon-carbon cathode material, step is:1) SiO is pressed2:Carbon source:Water=(30~80):(5~15):The mass ratio of (60~120), is made into slurries, 4~5h of wet grinding, and freeze-drying obtains nano level SiO2;2) by 1) gains high temperature cabonization, SiO is obtained2@C-materials, according still further to SiO2@C:Mg:NaCl mass ratioes 1:1:1~1:1:10 ratio, the magnesiothermic reduction at 600~750 DEG C, pickling later, washing, dry Si@C nano particles;3) by nano particle and graphene oxide solution ultrasound mixing 2), material is made in spray pyrolysis cladding reduction.The present invention is of low cost, easy to operate, is not easy to reunite, can maintain sample original appearance, product structure stability is good, and the electric conductivity and ion transport capability of material are strong.

Description

The method for preparing silicon-carbon cathode material based on micron silica
Technical field
The invention belongs to silicon-carbon cathode material preparation fields, and in particular to one kind preparing silicon-carbon based on micron silica and bears The method of pole material.
Background technology
Silica-base material right and wrong have hitherto known highest reason often with potential high performance lithium ionic cell cathode material By specific capacity (4200mAh/g) and lower intercalation potential (0.1Vvs.Li/Li+), and it is resourceful, it is environmental-friendly.But Silicium cathode, with huge volume change (up to 300%), can cause silicon particle to be crushed, dusting, make electricity during removal lithium embedded Pole material loses electroactive, shows as very poor cyclical stability;In addition, the conductivity of silicon itself is not high, multiplying power property is poor, This has seriously affected application of the silicon materials as lithium ion battery negative material.Si-C composite material is made to alleviate the above problems Effective way has obtained extensive research.Yu Xiaolei (preparation of lithium ion battery high performance silicon carbon compound cathode materials and property Can study, Shanghai Communications University's Master's thesis, 2013) it is two different using nano silica fume and mesoporous silicon oxide (SBA-15) Silicon source is prepared for spherical porous silicon/graphene@carbon (Si/GNS@C) composite material, but packet carbon method therein is chemistry Vapour deposition process, this method are not easy industrial application;(magnesium reduction process prepares porous silicon-carbon composite cathode to the superfine people of Tao Hua Material,《Silicate journal》08 phase in 2013) with mesoporous SiO2Silicon carbon material is prepared for the direct magnesiothermic reduction of silicon source, due to Nanoscale SiO2Preparation rely on mostly biomass silicon source or ethyl orthosilicate (TEOS) hydrolysis be made, and formed particle hold Easily reunite, causes manufacturing cost high, magnesium thermit effect is undesirable.
Invention content
For overcome the deficiencies in the prior art, the present invention provides prepare silicon-carbon cathode material based on micron silica There is method at low cost, easy industrialized production, the small product size of preparation to expand advantage small, that electric conductivity is strong.
In order to achieve the above object, the technical solution that the present invention takes is:
Based on the method that micron silica prepares silicon-carbon cathode material, include the following steps:
Step 1:According to silica:Carbon source:Water=(30~80):(5~15):The mass ratio of (60~120), respectively Silica, carbon source and the water for measuring 50~100um of grain size are configured to slurries, using sand mill 4~5h of wet grinding, then freeze It is dried to obtain nano level SiO2
Step 2:Step 1 gains are subjected to high temperature cabonization, obtain SiO2@C-materials, then according to SiO2@C:Mg: NaCl mass ratioes are 1:1:1~1:1:10 ratio, magnesiothermic reduction under the conditions of 600~750 DEG C, pickling later, washing, drying Si@C nano particles are made;
Step 3:After Si@C nanos particle made from step 2 and graphene oxide solution ultrasound mixing, pass through spraying Pyrolysis technology carries out cladding reduction, and Si@C@G materials are made.
Further, the carbon source is one of glucose, phenolic resin, polyvinylpyrrolidone, polyacrylonitrile.
Further, the temperature of step 1 freeze-drying is -45 DEG C.
Further, the high temperature cabonization of step 2 carries out at 450~700 DEG C, and be carbonized 2~4h.
Further, the pickling described in step 2, washing process are:Impurity is removed using 2mol/L chlorohydric acid picklings, then is used 5% hydrofluoric acid wash 30min, removes unreacted SiO2, finally washed again to neutrality with deionized water, ethyl alcohol.
Further, the process of the cladding reduction described in step 3 is:Using spraying is ultrasonically formed, realizes and is granulated function, Again by spherical particle obtained with H2/ Ar gaseous mixtures are carrier gas, are passed through 600~800 DEG C of vertical tubular furnace and carry out cladding reduction Operation collects to obtain dry Si@C@G materials finally by electrostatic field.
Beneficial effects of the present invention:
The present invention utilizes micron order SiO2For raw material, material is prepared by wet grinding, it is of low cost, it is easy to operate, also It can overcome and rely on biomass silicon source or ethyl orthosilicate TEOS hydrolysis nano level SiO obtained2It is easy to reunite, causes to prepare Problem of high cost, later stage magnesium thermit effect is undesirable;And by Freeze Drying Technique, sample original appearance can be maintained, more There is Commercial Prospect.
Organic polymer carbon source is chosen, the porous SiO of three-dimensional porous structure cladding can be obtained after carbonization2@C-materials, pass through The amount for controlling fluxing agent NaCl, controls the generation of SiC, is conducive to the structural stability of the maintenance material in charge and discharge process, together When, macromolecule carbon source contributes to buffer volumes to expand.
Using spray pyrolysis by Si@CIt is compound with graphene, carry out secondary cladding.During ullrasonic spraying, Ke Yiyou The realization of effect is granulated function, obtains evengranular spherical particle;And graphene oxide is in carrier gas Ar/H2The reduction of gas Under, graphene is generated, is coated on Si@C-materials surface, the electric conductivity and ion transport capability of reinforcing material preferably improve silicon The disadvantage of sill electric conductivity difference, obtains the Si-C composite material of function admirable.
Description of the drawings
Fig. 1 is the grain size distribution after being sanded;
Fig. 2 is the X-ray diffractogram after magnesium heat under different NaCl additive amounts;
Fig. 3 is the grain size enlarged drawing after Si@C spray drying.
Specific implementation mode
With reference to specific embodiment, the present invention will be further described.
Embodiment 1
Weigh SiO230g, polyvinylpyrrolidone 5g and water 120mL are in sand mill, wet grinding 4h, after separation, Be placed in refrigerator freezing, in cooling driers in -45 DEG C under the conditions of be freeze-dried two days two nights.
Product after cold do is placed in tube furnace, 4h is calcined under the conditions of 450 DEG C in inert atmosphere, obtains SiO2@C materials Material, then according to SiO2@C:Mg:The mass ratio of NaCl is 1:1:1 ratio, magnesium heat is also in an inert atmosphere, under the conditions of 650 DEG C Former 4h washs 8h in the hydrochloric acid solution of 2M, removes magnesium thermit by-product;Mass fraction, which is added, in solution after pickling is 0.5h is washed in 5% hydrofluoric acid solution, removes the SiO not reacted completely2, washed, filtered with deionized water and ethanol solution It to neutrality, is placed in vacuum drying oven, 12h is dried in vacuo under the conditions of 80 DEG C, obtain Si@C composites.
According to mass ratio it is 10 by Si@C composites and graphene oxide:1 weighs, and is added in 20mL water, ultrasound 15min, be allowed to it is fully dispersed in aqueous solution.Using spray pyrolysis device, mixed liquor is sprayed in tube furnace, 800 DEG C H2/Under the reduction of Ar mixed carrier gas, restores and Si@C@G particles are made, be collected by electrostatic field.
Embodiment 2
Weigh SiO2With sand mill, wet grinding 4h is detached by 40g, polyvinylpyrrolidone 10g and water 120mL Afterwards, be placed in refrigerator freezing, in cooling driers in -45 DEG C under the conditions of be freeze-dried two days two nights.
Product after cold do is placed in tube furnace, 4h is calcined under the conditions of 450 DEG C in inert atmosphere, obtains SiO2@C materials Material, then according to SiO2@C:Mg:The mass ratio of NaCl is 1:1:1 ratio, magnesium heat is also in an inert atmosphere, under the conditions of 650 DEG C Former 4h washs 8h in the hydrochloric acid solution of 2M, removes magnesium thermit by-product;Mass fraction, which is added, in solution after pickling is 0.5h is washed in 5% hydrofluoric acid solution, removes the SiO not reacted completely2, washed, filtered with deionized water and ethanol solution It to neutrality, is placed in vacuum drying oven, 12h is dried in vacuo under the conditions of 80 DEG C, obtain Si@C composites.
According to mass ratio it is 10 by Si@C composites and graphene oxide:1 weighs, and is added in 20mL water, ultrasound 15min, be allowed to it is fully dispersed in aqueous solution.Using spray pyrolysis device, mixed liquor is sprayed in tube furnace, 800 DEG C H2Under the reduction of/Ar mixed carrier gas, restores and Si@C@G particles are made, be collected by electrostatic field.
Embodiment 3
Weigh SiO2In 60g, polyvinylpyrrolidone 5g and water 120mL and sand mill, wet grinding 4h, after separation, Be placed in refrigerator freezing, in cooling driers in -45 DEG C under the conditions of be freeze-dried two days two nights.
Product after cold do is placed in tube furnace, 4h is calcined under the conditions of 500 DEG C in inert atmosphere, obtains SiO2@C materials Material, then according to SiO2@C:Mg:The mass ratio of NaCl is 1:1:3 ratio, magnesium heat is also in an inert atmosphere, under the conditions of 650 DEG C Former 4h washs 8h in the hydrochloric acid solution of 2M, removes magnesium thermit by-product;Mass fraction, which is added, in solution after pickling is 0.5h is washed in 5% hydrofluoric acid solution, removes the SiO not reacted completely2, washed, filtered with deionized water and ethanol solution It to neutrality, is placed in vacuum drying oven, 12h is dried in vacuo under the conditions of 80 DEG C, obtain Si@C composites.
According to mass ratio it is 10 by Si@C composites and graphene oxide:1 weighs, and is added in 20mL water, ultrasound 15min, be allowed to it is fully dispersed in aqueous solution.Using spray pyrolysis device, mixed liquor is sprayed in tube furnace, 800 DEG C H2/Ar mixed carrier gas reduction under, restore and Si@C@G particles be made, be collected by electrostatic field.
Embodiment 4
Weigh SiO2In 80g, polyvinylpyrrolidone 5g and water 100mL and sand mill, wet grinding 5h, after separation, Be placed in refrigerator freezing, in cooling driers in -45 DEG C under the conditions of be freeze-dried two days two nights.
Product after cold do is placed in tube furnace, 3h is calcined under the conditions of 500 DEG C in inert atmosphere, obtains SiO2@C materials Material, then according to SiO2@C:Mg:The mass ratio of NaCl is 1:1:5 ratio, magnesium heat is also in an inert atmosphere, under the conditions of 700 DEG C Former 4h washs 8h in the hydrochloric acid solution of 2M, removes magnesium thermit by-product;Mass fraction, which is added, in solution after pickling is 0.5h is washed in 5% hydrofluoric acid solution, removes the SiO not reacted completely2, washed, filtered with deionized water and ethanol solution It to neutrality, is placed in vacuum drying oven, 12h is dried in vacuo under the conditions of 80 DEG C, obtain Si@C composites.
According to mass ratio it is 10 by Si@C composites and graphene oxide:1 weighs, and is added in 20mL water, ultrasound 15min, be allowed to it is fully dispersed in aqueous solution.Using spray pyrolysis device, mixed liquor is sprayed in tube furnace, 800 DEG C H2Under the reduction of/Ar mixed carrier gas, restores and Si@C@G particles are made, be collected by electrostatic field.
Embodiment 5
Weigh SiO2In 60g, polyvinylpyrrolidone 5g and water 100mL and sand mill, wet grinding 4h, after separation, Be placed in refrigerator freezing, in cooling driers in -45 DEG C under the conditions of be freeze-dried two days two nights.
Product after cold do is placed in tube furnace, 4h is calcined under the conditions of 450 DEG C in inert atmosphere, obtains SiO2@C materials Material, then according to SiO2@C:Mg:The mass ratio of NaCl is 1:1:10 ratio, in an inert atmosphere, magnesium heat under the conditions of 700 DEG C 4h is restored, 8h is washed in the hydrochloric acid solution of 2M, removes magnesium thermit by-product;Mass fraction, which is added, in solution after pickling is 0.5h is washed in 5% hydrofluoric acid solution, removes the SiO not reacted completely2, washed, filtered with deionized water and ethanol solution It to neutrality, is placed in vacuum drying oven, 12h is dried in vacuo under the conditions of 80 DEG C, obtain Si@C composites.
According to mass ratio it is 10 by Si@C composites and graphene oxide:1 weighs, and is added in 20mL water, ultrasound 15min, be allowed to it is fully dispersed in aqueous solution.Using spray pyrolysis device, mixed liquor is sprayed in tube furnace, 700 DEG C H2/Ar mixed carrier gas reduction under, restore and Si@C@G particles be made, be collected by electrostatic field.
Fig. 1 is the grain size distribution after being sanded, and has chosen the particle after 5h is sanded in embodiment 4 and carries out grain size test, knot Fruit shows that sand milling can make micron order SiO2Average particle size distribution in 200nm or so, there is preferable grinding effect.
Fig. 2 is the X-ray diffractogram after magnesium heat under different NaCl additive amounts, and the chart is bright, and the additive amount of NaCl can influence The generation of SiC, the increase of NaCl dosages are conducive to the reduction of SiC.
Fig. 3 is the grain size enlarged drawing after Si@C spray drying, it can be seen that forms fluffy sphere material, thus has Conducive to the volume expansion of alleviation material.

Claims (6)

1. the method for preparing silicon-carbon cathode material based on micron silica, which is characterized in that include the following steps:
Step 1:According to silica:Carbon source:Water=(30~80):(5~15):The mass ratio of (60~120), measures respectively Silica, carbon source and the water of 50~100um of grain size is configured to slurries, using sand mill 4~5h of wet grinding, then is freeze-dried Obtain nano level SiO2
Step 2:Step 1 gains are subjected to high temperature cabonization, obtain SiO2@C-materials, then according to SiO2@C:Mg:NaCl matter Amount is than being 1:1:1~1:1:10 ratio, magnesiothermic reduction under the conditions of 600~750 DEG C, pickling later, washing, drying are made Si@C nano particles;
Step 3:After Si@C nanos particle made from step 2 and graphene oxide solution ultrasound mixing, pass through spray pyrolysis Solution technology carries out cladding reduction, and Si@C@G materials are made.
2. the method for preparing silicon-carbon cathode material based on micron silica as described in claim 1, which is characterized in that described Carbon source is one of glucose, phenolic resin, polyvinylpyrrolidone, polyacrylonitrile.
3. the method for preparing silicon-carbon cathode material based on micron silica as described in claim 1, which is characterized in that step The temperature of one freeze-drying is -45 DEG C.
4. the method for preparing silicon-carbon cathode material based on micron silica as described in claim 1, which is characterized in that step Two high temperature cabonization carries out at 450~700 DEG C, and be carbonized 2~4h.
5. the method for preparing silicon-carbon cathode material based on micron silica as described in claim 1, which is characterized in that step Pickling, washing process described in two are:Impurity is removed using 2mol/L chlorohydric acid picklings, then with 5% hydrofluoric acid wash 30min, Remove unreacted SiO2, finally washed again to neutrality with deionized water, ethyl alcohol.
6. the method for preparing silicon-carbon cathode material based on micron silica as described in claim 1, which is characterized in that step Described in three cladding reduction process be:Using be ultrasonically formed spraying, realize be granulated function, then by spherical particle obtained with H2/ Ar gaseous mixtures are carrier gas, are passed through 600~800 DEG C of vertical tubular furnace and carry out cladding reduction operation, are received finally by electrostatic field Collection obtains dry Si@C@G materials.
CN201810219122.8A 2018-03-16 2018-03-16 Method for preparing silicon-carbon negative electrode material based on micron silicon dioxide Active CN108470891B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109399601A (en) * 2018-09-14 2019-03-01 江苏大学 A kind of preparation method and purposes of nitrogen-phosphor codoping biological carbon materials
CN113036137A (en) * 2021-03-05 2021-06-25 昆山宝创新能源科技有限公司 Lithium ion battery cathode material and preparation method and application thereof
CN113998702A (en) * 2021-10-13 2022-02-01 昆明理工大学 Method for preparing Si/C negative electrode material by using micro silicon powder as raw material
WO2022121137A1 (en) * 2020-12-10 2022-06-16 广东凯金新能源科技股份有限公司 One-dimensional porous silicon-carbon composite negative electrode material, preparation method, and application thereof

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CN105958036A (en) * 2016-07-07 2016-09-21 天津普兰能源科技有限公司 Preparation method for carbon-coated silicon negative electrode material for lithium ion battery
CN106374088A (en) * 2016-10-14 2017-02-01 浙江天能能源科技股份有限公司 Method for preparing silicon/carbon composite material with magnesiothermic reduction process
CN106848273A (en) * 2017-01-19 2017-06-13 深圳市沃特玛电池有限公司 A kind of preparation method of Si-C composite material
CN107240677A (en) * 2016-03-28 2017-10-10 国家纳米科学中心 A kind of micro-nano structure carbon silicon complex microsphere and its production and use

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Publication number Priority date Publication date Assignee Title
CN107240677A (en) * 2016-03-28 2017-10-10 国家纳米科学中心 A kind of micro-nano structure carbon silicon complex microsphere and its production and use
CN105958036A (en) * 2016-07-07 2016-09-21 天津普兰能源科技有限公司 Preparation method for carbon-coated silicon negative electrode material for lithium ion battery
CN106374088A (en) * 2016-10-14 2017-02-01 浙江天能能源科技股份有限公司 Method for preparing silicon/carbon composite material with magnesiothermic reduction process
CN106848273A (en) * 2017-01-19 2017-06-13 深圳市沃特玛电池有限公司 A kind of preparation method of Si-C composite material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109399601A (en) * 2018-09-14 2019-03-01 江苏大学 A kind of preparation method and purposes of nitrogen-phosphor codoping biological carbon materials
CN109399601B (en) * 2018-09-14 2021-12-21 江苏大学 Preparation method and application of nitrogen-phosphorus co-doped biochar material
WO2022121137A1 (en) * 2020-12-10 2022-06-16 广东凯金新能源科技股份有限公司 One-dimensional porous silicon-carbon composite negative electrode material, preparation method, and application thereof
CN113036137A (en) * 2021-03-05 2021-06-25 昆山宝创新能源科技有限公司 Lithium ion battery cathode material and preparation method and application thereof
CN113998702A (en) * 2021-10-13 2022-02-01 昆明理工大学 Method for preparing Si/C negative electrode material by using micro silicon powder as raw material
CN113998702B (en) * 2021-10-13 2023-10-13 昆明理工大学 Method for preparing Si/C anode material by taking micro silicon powder as raw material

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