CN103050668B - Method for preparing Si/C composite cathode material for lithium ion battery - Google Patents
Method for preparing Si/C composite cathode material for lithium ion battery Download PDFInfo
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- CN103050668B CN103050668B CN201210567170.9A CN201210567170A CN103050668B CN 103050668 B CN103050668 B CN 103050668B CN 201210567170 A CN201210567170 A CN 201210567170A CN 103050668 B CN103050668 B CN 103050668B
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Abstract
The invention discloses a method for preparing a silicon/carbon (Si/C) composite cathode material for a lithium ion battery. The method comprises the steps that graphite and a metal salt additive agent are uniformly dispersed in a concentrated sulfuric acid solution; micro graphite oxide is prepared through an oxidation reaction; the obtained micro graphite oxide and a silicon source are dispersed in a solution dissolved with a carbon source and an organic additive agent, after ultrasonic dispersion and uniform mixing, suspension liquid is formed, after the suspension liquid is evaporated to dryness, the heat treatment is performed at the temperature in a range from 600 DEG C to 1000 DEG C, and then the Si/C composite cathode material is formed. The method is simple and easy to implement, the practicability degree is high, and the prepared composite material has the advantages that the shape is good, the tap density and capacity are high, the cycle performance and multiplying power performance are good, and the like.
Description
Technical field
The invention belongs to lithium ion battery material and preparation method thereof field, relate to a kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery is because of himself inherent advantages, as large in energy density, operating voltage is high, long service life, be easy to carry, and is widely used in portable electric appts and electric automobile.Business-like graphite as anode material for lithium-ion battery is because of its capacity limit (372mAhg
-1) demand of high energy density cells can not be met gradually.Therefore the Novel anode material of the alternative graphite of exploitation receives much concern.
Silica-base material is because having most height ratio capacity (4200mAhg
-1), low removal lithium embedded current potential (0.02 ~ 0.6V vs.Li
+/ Li) and be considered to optimum wish to improve improve one of material of lithium ion battery negative material performance.But the volumetric expansion serious in removal lithium embedded process of silicium cathode and contraction (>300%), cause destruction and the mechanical crushing of material structure, thus limit its commercial applications.For improving these problems, at present mainly through by silicon nanometer, silicon and metallic alloying, just the mode such as silicon and active or nonactive matrix composite is to improve its performance to prepare silicon thin film, wherein Si-C composite material has better application prospect.In Si-C composite material, carbon is the mixed conductor of ion and electronics, " cushioning frame " that material with carbon element is formed can compensate the volumetric expansion of silicon grain, in charge and discharge process, change in volume is little, can the structural stability of maintenance electrode material and good conductivity, thus the cycle performance of silica-base material is improved.In addition, the intercalation potential of material with carbon element and silicon is close, and material capacity loss is relatively little.
Summary of the invention
The object of the invention is to be to provide a kind of and simple and quickly prepare that pattern is good, tap density is high, capacity is high, the method for the silicon-carbon composite cathode material of lithium ion battery of cyclicity and good rate capability.
The invention provides a kind of preparation method of lithium ion battery Si/C composite negative pole material, the method is dispersed in concentrated sulfuric acid solution by graphite and metallic salt additive; First at not higher than 2 DEG C, add oxidant reaction, react in 32 ~ 38 DEG C again, deionized water dilute reaction solution is used after reacting completely, or first add oxidant reaction being not more than at 2 DEG C, react in 32 ~ 38 DEG C again, then use deionized water dilute reaction solution, then continue reaction at 92 ~ 98 DEG C, continue after having reacted spend ionized water dilute reaction solution and add hydrogen peroxide; By the diluted reactant liquor Separation of Solid and Liquid finally obtained, it is 3 ~ 4 that the solid watery hydrochloric acid that separation obtains and deionized water are washed till pH value, obtains low-level oxidation graphite after dry; Be dispersed in the solution being dissolved with carbon source and organic additive by the low-level oxidation graphite of acquisition and silicon source, ultrasonic disperse, obtains suspension after stirring and evenly mixing, and after suspension evaporate to dryness, heat-treats, to obtain final product at 600 ~ 1000 DEG C; Wherein silicon source: graphite: after carbon source pyrolysis, the mass ratio of gained RESEARCH OF PYROCARBON is x:y:(1-x-y), wherein 0<x<1,0 < y<1; The addition in silicon source accounts for 5 ~ 30wt.% of Si/C composite material, and the addition of carbon source counts 10 ~ 50wt.% of Si/C composite material with gained RESEARCH OF PYROCARBON after heat treatment.
The preparation of low-level oxidation graphite in above-mentioned preparation method: first add oxidant reaction 0.3 ~ 0.8h at not higher than 2 DEG C, then 1 ~ 3h is reacted at 32 ~ 38 DEG C; Or first at not higher than 2 DEG C, add oxidant reaction 0.3 ~ 0.8h, then 1 ~ 3h is reacted at 32 ~ 38 DEG C, then reaction 1 ~ 3h is continued at 92 ~ 98 DEG C; As required by the degree of graphite oxidation, carry out the mode of Selective Oxidation.
Described hydrogen peroxide consumption is 0.5 ~ 10 times of graphite quality; Deionized water consumption is 1 ~ 5 times of concentrated sulfuric acid volume.
Described graphite comprises: one or more in electrographite, native graphite or graphitized intermediate-phase carbosphere.
Described silicon source comprises: one or more in nano silica fume, silica powder, carbon-coated nano silica flour, the coated silica powder of carbon, and wherein silica powder is SiO
x, O < x≤2.
Described carbon source comprises: one or more in Graphene, phenolic resins, Lauxite, epoxy resin, polyethylene, chlorinated polyvinyl chloride, polyvinyl alcohol, pitch, glucose, citric acid or sucrose.
Described oxidant is one or more in hydrogen peroxide, potassium bichromate or potassium permanganate; Wherein the consumption of hydrogen peroxide is 0.5 ~ 20 times of graphite quality, and the consumption of potassium bichromate is 1.5 ~ 2.5 times of graphite quality, and the consumption of potassium permanganate is 0.5 ~ 4 times of graphite quality.
Described heat treatment processes 1 ~ 6h in argon gas or nitrogen environment.
Solvent in the described solution being dissolved with carbon source and organic additive is one or more in deionized water, oxolane, acetone, pyrroles, ethyl acetate or absolute ethyl alcohol.
Described Separation of Solid and Liquid be by dilution after solution left standstill after isolated by filtration or centrifugation; Suspension evaporate to dryness mode comprises one or more in evaporation curable, vacuumize or spraying dry.
Described Metal Salts is one or more in sodium nitrate or potassium nitrate.
Described organic additive comprises: one or more in polyacrylamide, polyethylene glycol, propylene glycol, polyvinyl acetate, N-N dimethylacetylamide, sodium alginate, neopelex, cetyl amine bromide or absolute ethyl alcohol.
The temperature of described evaporation curable is 70 ~ 120 DEG C; Spray drying temperature is 170 ~ 200 DEG C; Vacuum drying temperature is 60 ~ 90 DEG C.
The technology of the present invention feature: adopt liquid phase process to prepare low-level oxidation graphite, have good pattern, gained low-level oxidation graphite is loose structure, for establishing good basis with the combination in silicon source; Prepare Si/C negative material on this basis, the Si/C composite material of preparation has good pattern, and silicon source can better be combined with graphite, and forms uniform carbon coating layer on its surface; This structure is conducive to the raising of the intensity of material, the increase of toughness and tap density; This method possesses, simple operation and other advantages strong to adaptability to raw material simultaneously.
The beneficial effect that the present invention has is:
Low-level oxidation graphite comprehensive silicon carbon compound cathode materials of the present invention, has the following advantages: by carrying out low-level oxidation process to graphite, change its pattern and surface activity, for hole is reserved in the embedding of silicon, for setting up basis with the combination in granule silicon source.On this basis, part silicon source is embedded in low-level oxidation graphite hole, is better combined with low-level oxidation graphite simultaneously, and carbon source forms the coating layer of packed uniform at composite material surface by pyrolysis.In pyrolytic process, carbon source can not be pure liquid state, can not fill in silicon and the remaining all holes of low-level oxidation graphite compound, define good " cushioning frame ", and the existence of RESEARCH OF PYROCARBON material simultaneously enhances the electric conductivity of material.Therefore, the structural stability that composite material can significantly improve the intensity of Si/C composite material, toughness enhances material of preparation, alleviate the avalanche degree of silicon based anode material electrode structure in charge and discharge process to a certain extent, improve the conductivity of Si/C composite material simultaneously, thus enhance cyclical stability and the high rate performance of material.
Be multi-pore structure by liquid phase oxidation gained low-level oxidation graphite, therefore for provide better compound hole with the compound of silicon, on the coated basis of carbon source, spherical or irregular particle is obtained, improve the tap density of material, thus energy density also lifting to a certain extent.
In Si/C composite material, silicon source: graphite: RESEARCH OF PYROCARBON mass ratio=x:y:(1-x-y), wherein silicon source capacity is higher (if nano silica fume is 4200mAhg
-1), be the critical active material determining composite material capacity, therefore by adjustment silicon source component and proportion in the composite, high power capacity Si/C composite negative pole material can be obtained.
Accompanying drawing explanation
[Fig. 1] is the SEM figure of low-level oxidation native graphite for the SEM figure of native graphite before and after liquid phase low-level oxidation, a are the SEM figure of native graphite, b.
The SEM that [Fig. 2] is the embodiment of the present invention 2 schemes: a is the SEM figure of nano silica fume in embodiment 2, b is that the SEM of the coated rear nano silica fume of carbon in embodiment 2 schemes; C is the SEM figure preparing Si/C composite negative pole material in embodiment 2.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.Following embodiment is intended to the present invention instead of limitation of the invention further are described.
Embodiment 1
Measure dense H
2sO
4solution 120mL, after adding appropriate potassium nitrate and 10g native graphite, is positioned in 0 DEG C of ice bath, magnetic agitation 0.5h in this solution; The potassium permanganate taking a certain amount of 5 ~ 20g joins in above-mentioned feed liquid slowly, in 38 DEG C after temperature reaction 1.5h, slowly adds a large amount of deionized waters and is diluted to about 1L, and control feed temperature below 100 DEG C; Filter after leaving standstill, being washed till pH value with a large amount of absolute ethyl alcohol and deionized water is 3 ~ 4, dry for standby, and before and after oxidation, graphite morphology as shown in Figure 1.Taking 1g nano silica fume, 2g low-level oxidation graphite and 5g glucose by composite Materials Design capacity is dissolved in appropriate amount of deionized water, using 0.15g cetyl amine bromide as dispersant, ultrasonic 1h, carry out vacuumize after stirring, after gained solid proceeds to and carries out high-temperature process 1 ~ 6h in 800 DEG C in temperature programmed control stove in nitrogen or argon gas atmosphere, obtain Si/C composite negative pole material.
Embodiment 2
Measure the dense H of 200mL
2sO
4solution, after adding appropriate potassium nitrate and 5g natural graphite powder, is positioned in 0 DEG C of ice bath, magnetic agitation 0.5h in this solution; Taking 5 ~ 20g potassium permanganate joins in above-mentioned feed liquid slowly, controls reaction temperature below 2 DEG C, in 35 DEG C after temperature reaction 2h, slowly adds a large amount of deionized waters and is diluted to about 0.6L, and control feed temperature below 100 DEG C; Then at 95 DEG C, add appropriate hydrogen peroxide and 400 ~ 800mL deionized water after pyroreaction 2h, centrifugation, and to be washed till pH value with a large amount of absolute ethyl alcohol and deionized water be 3 ~ 4, freeze-dried back.In nano-silicon Surface coating 10% glucose RESEARCH OF PYROCARBON, coated front and back pattern is as shown in Fig. 2 (a) and Fig. 2 (b), taking 1g nano silica fume, 2g low-level oxidation graphite and 1.67g glucose by composite Materials Design capacity is dissolved in appropriate amount of deionized water, 0.15g neopelex is as dispersant, ultrasonic 1h, spraying dry is carried out after stirring, Si/C composite negative pole material is obtained, as shown in Figure 2 (c) after gained solid proceeds to and carries out high temperature place 1 ~ 6h in 800 DEG C in temperature programmed control stove in nitrogen or argon gas atmosphere.
Embodiment 3
Measure dense H
2sO
4solution, after adding appropriate sodium nitrate and 10g natural graphite powder, is positioned in 0 DEG C of ice bath, magnetic agitation 0.5h in this solution; Taking 15 ~ 25g potassium bichromate joins in above-mentioned feed liquid slowly, in 38 DEG C after temperature reaction 1.5h, slowly adds a large amount of deionized waters and is diluted to about 1L, and control feed temperature below 100 DEG C; Filter after leaving standstill, being washed till pH value with a large amount of absolute ethyl alcohol and deionized water is 3 ~ 4, dry for standby.Taking nano silica fume, low-level oxidation graphite and phenolic resins by composite Materials Design capacity is dissolved in appropriate absolute ethyl alcohol, ultrasonic 1h, at 80 DEG C of evaporates to dryness after stirring 2h, proceed to after gained solid drying after carrying out high temperature place 1 ~ 6h in 800 DEG C in temperature programmed control stove in nitrogen or argon gas atmosphere and obtain Si/C composite negative pole material.
Claims (7)
1. a preparation method for lithium ion battery Si/C composite negative pole material, is characterized in that, is dispersed in concentrated sulfuric acid solution by graphite and metallic salt additive; First at not higher than 2 DEG C, add oxidant reaction 0.3 ~ 0.8h, 1 ~ 3h is reacted again in 32 ~ 38 DEG C, deionized water dilute reaction solution is used after reacting completely, or first add oxidant reaction 0.3 ~ 0.8h being not more than at 2 DEG C, 1 ~ 3h is reacted again in 32 ~ 38 DEG C, then use deionized water dilute reaction solution, then continue reaction 1 ~ 3h at 92 ~ 98 DEG C, continue after having reacted spend ionized water dilute reaction solution and add hydrogen peroxide; By the diluted reactant liquor Separation of Solid and Liquid finally obtained, it is 3 ~ 4 that the solid watery hydrochloric acid that separation obtains and deionized water are washed till pH value, obtains low-level oxidation graphite after dry; Be dispersed in the solution being dissolved with carbon source and organic additive by the low-level oxidation graphite of acquisition and silicon source, ultrasonic disperse, obtains suspension after stirring and evenly mixing, and after suspension evaporate to dryness, heat-treats, to obtain final product at 600 ~ 1000 DEG C; Wherein silicon source: graphite: after carbon source pyrolysis, the mass ratio of gained RESEARCH OF PYROCARBON is x:y:(1-x-y), wherein 0<x<1,0<y<1; The addition in silicon source accounts for 5 ~ 30wt.% of Si/C composite material, and the addition of carbon source counts 10 ~ 50wt.% of Si/C composite material with gained RESEARCH OF PYROCARBON after heat treatment; Described oxidant is potassium bichromate or potassium permanganate, when adopting potassium permanganate as oxidant, the addition of potassium permanganate is 0.5 ~ 4 times of graphite quality, and when adopting potassium bichromate as oxidant, the addition of potassium bichromate is 1.5 ~ 2.5 times of graphite quality; Described hydrogen peroxide consumption is 0.5 ~ 10 times of graphite quality; Deionized water consumption is 1 ~ 5 times of concentrated sulfuric acid volume.
2. preparation method according to claim 1, is characterized in that, described graphite comprises: one or more in electrographite, native graphite or graphitized intermediate-phase carbosphere.
3. preparation method according to claim 1, is characterized in that, described silicon source comprises: one or more in nano silica fume, silica powder, carbon-coated nano silica flour, the coated silica powder of carbon, and wherein silica powder is SiO
x, described SiO
xthe span of middle x is 0 < x≤2; Described carbon source comprises: one or more in Graphene, phenolic resins, Lauxite, epoxy resin, polyethylene, chlorinated polyvinyl chloride, polyvinyl alcohol, pitch, glucose, citric acid or sucrose.
4. preparation method according to claim 1, is characterized in that, described heat treatment processes 1 ~ 6h in argon gas or nitrogen environment.
5. preparation method according to claim 1, is characterized in that, described in the solvent be dissolved with in the solution of carbon source and organic additive be one or more in deionized water, oxolane, acetone, pyrroles, ethyl acetate or absolute ethyl alcohol.
6. preparation method according to claim 1, is characterized in that, described Separation of Solid and Liquid be by dilution after solution left standstill after isolated by filtration or centrifugation; Suspension evaporate to dryness mode comprises one or more in evaporation curable, vacuumize or spraying dry.
7. preparation method according to claim 1, is characterized in that, described Metal Salts is one or more in sodium nitrate or potassium nitrate; Described organic additive comprises: one or more in polyacrylamide, polyethylene glycol, propylene glycol, polyvinyl acetate, N-N dimethylacetylamide, sodium alginate, neopelex, cetyl amine bromide or absolute ethyl alcohol.
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Families Citing this family (12)
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| CN104282894B (en) * | 2013-07-08 | 2016-08-17 | 北京化工大学 | A kind of preparation method of porous Si/C complex microsphere |
| CN104852023A (en) * | 2015-04-01 | 2015-08-19 | 廖楚宏 | Carbon composite material and preparation method therefor |
| CN105336953B (en) * | 2015-09-30 | 2017-11-10 | 广西师范大学 | A kind of preparation method of the graphitized intermediate-phase carbosphere negative material of surface controllable oxidization |
| CN105514381A (en) * | 2015-12-25 | 2016-04-20 | 苏州格瑞动力电源科技有限公司 | Method for treating silicon negative materials of lithium ion battery |
| CN105576241B (en) * | 2016-03-02 | 2017-11-17 | 中国科学院山西煤炭化学研究所 | Preparation method for silicon/carbon composite of high performance lithium ionic cell cathode |
| CN107768607B (en) * | 2016-08-15 | 2020-10-16 | 福建新峰二维材料科技有限公司 | Preparation method of lithium ion battery negative electrode material |
| CN107068996B (en) * | 2017-02-27 | 2019-10-25 | 陕西六元碳晶股份有限公司 | A kind of continuous preparation method of silicon-carbon nitrogen composite material |
| CN107123805A (en) * | 2017-06-29 | 2017-09-01 | 中能国盛动力电池技术（北京）股份公司 | A kind of nano-silicone wire/carbon composite material and preparation method thereof |
| CN108172785B (en) * | 2017-12-22 | 2020-11-24 | 东莞东阳光科研发有限公司 | Carbon/silicon/carbon composite material and preparation method and application thereof |
| CN108963258A (en) * | 2018-07-11 | 2018-12-07 | 大同新成新材料股份有限公司 | A kind of porous carbon-based negative electrode material of surface low-level oxidation and preparation method thereof |
| CN111063875A (en) * | 2019-12-25 | 2020-04-24 | 广东凯金新能源科技股份有限公司 | Spongy porous structure silicon-based composite material and preparation method thereof |
| CN111628153A (en) * | 2020-06-20 | 2020-09-04 | 沈晨 | Novel lithium ion battery cathode material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569756A (en) * | 2011-12-27 | 2012-07-11 | 上海交通大学 | Preparation method of silicon/graphene nanocomposite material for cathode of lithium ion battery |
-
2012
- 2012-12-24 CN CN201210567170.9A patent/CN103050668B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569756A (en) * | 2011-12-27 | 2012-07-11 | 上海交通大学 | Preparation method of silicon/graphene nanocomposite material for cathode of lithium ion battery |
Non-Patent Citations (4)
| Title |
|---|
| Graphene/nanosized silicon composites for lithium battery anodes with improved cycling stability;Hongfa Xiang等;《Carbon》;20110430;第49卷(第5期);第1787-1796页 * |
| Preparation and characterization of flake graphite/silicon/carbon spherical composite as anode materials for lithium-ion batteries;第530卷;《Journal of Alloys and Compounds》;20120725;第530卷;第30-35页 * |
| Preparation of Graphitic Oxide;William S.Hummers,JR等;《Journal of the American Chemical Society》;19580320;第80卷(第6期);第1339-1339页 * |
| 锂离子电池用硅/石墨/碳复合负极材料的电化学性能;亓鹏等;《功能材料》;20120315;第43卷(第5期);第657-659页 * |
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