CN103050668A - 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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- CN103050668A CN103050668A CN2012105671709A CN201210567170A CN103050668A CN 103050668 A CN103050668 A CN 103050668A CN 2012105671709 A CN2012105671709 A CN 2012105671709A CN 201210567170 A CN201210567170 A CN 201210567170A CN 103050668 A CN103050668 A CN 103050668A
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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, and is large such as energy density, operating voltage is high, long service life, be easy to carry etc., is widely used in portable electric appts and the electric automobile.Business-like graphite as anode material for lithium-ion battery is because of its capacity limit (372mAhg
-1) can not satisfy gradually the demand of high energy density cells.Therefore the Novel anode material of the alternative graphite of exploitation receives much concern.
Silica-base material is because having height ratio capacity (4200mAhg
-1), low removal lithium embedded current potential (0.02 ~ 0.6V vs.Li
+/ Li) being considered to optimum hope raising improves one of material of lithium ion battery negative material performance.Yet silicium cathode serious volumetric expansion and contraction (〉 300% in the removal lithium embedded process), cause destruction and the mechanical crushing of material structure, thereby limited its commercial applications.For improving these problems, mainly by silicon nanometer, silicon and metal alloy, the preparation silicon thin film modes such as just silicon and active or nonactive matrix is compound are improved its performance, wherein Si-C composite material has better application prospect at present.In the Si-C composite material, carbon is the mixed conductor of ion and electronics, " the buffering skeleton " that material with carbon element consists of can compensate the volumetric expansion of silicon grain, change in volume is little in charge and discharge process, can keep the structural stability of electrode material and good conductivity, thereby so that the cycle performance of silica-base material improve.In addition, the embedding lithium current potential of material with carbon element and silicon is close, material capacity loss less.
Summary of the invention
The objective of the invention is to be to provide that a kind of Simple fast prepares 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 that graphite and metallic salt additive are dispersed in the concentrated sulfuric acid solution; Be not higher than 2 ℃ of lower oxidant reactions that add first, again reaction in 32 ~ 38 ℃, the rear deionized water dilute reaction solution of using reacts completely, perhaps be not more than 2 ℃ of lower oxidant reactions that add first, again reaction in 32 ~ 38 ℃, then use the deionized water dilute reaction solution, react 92 ~ 98 ℃ of lower continuation again, continue to spend the ionized water dilute reaction solution and add hydrogen peroxide after reaction is finished; With the reactant liquor Separation of Solid and Liquid of the dilution that obtains at last, separating the solid that obtains, to be washed till pH value with watery hydrochloric acid and deionized water be 3 ~ 4, dry afterwards acquisition low-level oxidation graphite; The low-level oxidation graphite and the silicon source that obtain are dispersed in the solution that is dissolved with carbon source and organic additive, and ultrasonic dispersion obtains suspension after stirring and evenly mixing, and behind the suspension evaporate to dryness, heat-treats under 600 ~ 1000 ℃, and get final product; Silicon source wherein: graphite: the mass ratio of gained RESEARCH OF PYROCARBON is x:y:(1-x-y after the carbon source pyrolysis), 0＜x＜1,0＜y＜1 wherein; The addition in silicon source accounts for 5 ~ 30wt.% of Si/C composite material, the addition of carbon source with heat treatment after the gained RESEARCH OF PYROCARBON count 10 ~ 50wt.% of Si/C composite material.
The preparation of low-level oxidation graphite among the above-mentioned preparation method: first not being higher than 2 ℃ of lower oxidant reaction 0.3 ~ 0.8h that add, again at 32 ~ 38 ℃ of lower reaction 1 ~ 3h; Or first not being higher than 2 ℃ of lower oxidant reaction 0.3 ~ 0.8h that add, again at 32 ~ 38 ℃ of lower reaction 1 ~ 3h, again at 92 ~ 98 ℃ of lower reaction 1 ~ 3h that continue; With the degree of graphite oxidation, come the mode of Selective Oxidation as required.
Described hydrogen peroxide consumption is 0.5 ~ 10 times of graphite quality; The deionized water consumption is 1 ~ 5 times of concentrated sulfuric acid volume.
Described graphite comprises: one or more in electrographite, native graphite or the graphitized intermediate-phase carbosphere.
Described silicon source comprises: nano silica fume, silica powder, carbon-coated nano silica flour, carbon coat one or more in the silica powder, 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 the sucrose.
Described oxidant is one or more in hydrogen peroxide, potassium bichromate or the 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 is to process 1 ~ 6h in argon gas or nitrogen environment.
Solvent in the described solution that is dissolved with carbon source and organic additive is one or more in deionized water, oxolane, acetone, pyrroles, ethyl acetate or the absolute ethyl alcohol.
Described Separation of Solid and Liquid is isolated by filtration or centrifugation behind the solution left standstill after will diluting; Suspension evaporate to dryness mode comprises one or more in evaporation curing, vacuumize or the spray drying.
Described Metal Salts is one or more in sodium nitrate or the 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 the absolute ethyl alcohol.
The temperature that described evaporation is solidified is 70 ~ 120 ℃; The spray drying temperature is 170 ~ 200 ℃; Vacuum drying temperature is 60 ~ 90 ℃.
The technology of the present invention feature: adopt liquid phase to process preparation low-level oxidation graphite, have good pattern, gained low-level oxidation graphite is loose structure, for having set up good basis with the combination in silicon source; Prepare on this basis the Si/C negative material, the Si/C composite material of preparation has good pattern, can better be combined with graphite in the silicon source, and forms uniform carbon coating layer on its surface; This structure is conducive to the intensity of material, the increase of toughness and the raising of 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: process by graphite being carried out low-level oxidation, change its pattern and surface activity, for hole is reserved in the embedding of silicon, for setting up the basis with the combination in granule silicon source.On this basis, part silicon source is embedded in the low-level oxidation graphite hole, and with the better combination of low-level oxidation graphite, carbon source forms closely knit uniform coating layer by pyrolysis at composite material surface simultaneously.In pyrolytic process, carbon source can not be pure liquid state, can not fill in compound remaining all holes of silicon and low-level oxidation graphite, has formed good " buffering skeleton ", and the simultaneously existence of RESEARCH OF PYROCARBON material has strengthened the electric conductivity of material.Therefore, intensity, the toughness that the composite material of preparation can obviously improve the Si/C composite material has strengthened the structural stability of material, alleviated to a certain extent the avalanche degree of silicon based anode material electrode structure in charge and discharge process, improve simultaneously the conductivity of Si/C composite material, thereby strengthened cyclical stability and the high rate performance of material.
Be multi-pore structure by liquid phase oxidation gained low-level oxidation graphite, therefore for providing better compound hole with silicon compound, coat on the basis in carbon source, obtain sphere or irregular particle, improved the tap density of material, thus energy density also lifting to a certain extent.
In the Si/C composite material, silicon source: graphite: RESEARCH OF PYROCARBON mass ratio=x:y:(1-x-y), wherein silicon source capacity is higher (is 4200mAhg such as nano silica fume
-1), be the crucial active material that determines the composite material capacity, therefore can reach proportion in composite material by adjusting silicon source component, obtain high power capacity Si/C composite negative pole material.
Description of drawings
[Fig. 1] is the SEM figure of native graphite before and after the liquid phase low-level oxidation, and a is the SEM figure of native graphite, and b is the SEM figure of low-level oxidation native graphite.
[Fig. 2] is the SEM figure of nano silica fume among the embodiment 2 for the SEM figure of the embodiment of the invention 2: a, and b is the SEM figure of nano silica fume after carbon coats among the embodiment 2; C is the SEM figure of preparation Si/C composite negative pole material among the embodiment 2.
Embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments.Following embodiment is intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1
Measure dense H
2SO
4Solution 120mL, add an amount of potassium nitrate and 10g native graphite in this solution after, be positioned in 0 ℃ of ice bath magnetic agitation 0.5h; The potassium permanganate that takes by weighing a certain amount of 5 ~ 20g joins in the above-mentioned feed liquid slowly, behind the temperature reaction 1.5h, slowly add a large amount of deionized waters and be diluted to about 1L in 38 ℃, and the control feed temperature is below 100 ℃; Leave standstill rear filtration, being washed till the pH value with a large amount of absolute ethyl alcohols and deionized water is 3 ~ 4, dry for standby, and graphite morphology is as shown in Figure 1 before and after the oxidation.Taking by weighing 1g nano silica fume, 2g low-level oxidation graphite and 5g glucose by the composite Materials Design capacity is dissolved in the appropriate amount of deionized water, with 0.15g cetyl amine bromide as dispersant, ultrasonic 1h, carry out vacuumize after stirring, the gained solid change in the temperature programmed control stove in nitrogen or argon gas atmosphere in 800 ℃ after carrying out high-temperature process 1 ~ 6h the Si/C composite negative pole material.
Embodiment 2
Measure the dense H of 200mL
2SO
4Solution, add an amount of potassium nitrate and 5g natural graphite powder in this solution after, be positioned in 0 ℃ of ice bath magnetic agitation 0.5h; Take by weighing 5 ~ 20g potassium permanganate and join slowly in the above-mentioned feed liquid, the control reaction temperature behind the temperature reaction 2h, slowly adds a large amount of deionized waters and be diluted to about 0.6L in 35 ℃, and the control feed temperature is below 100 ℃ below 2 ℃; Then behind 95 ℃ of lower pyroreaction 2h, add an amount of hydrogen peroxide and 400 ~ 800mL deionized water, centrifugation, and to be washed till the pH value with a large amount of absolute ethyl alcohols and deionized water be 3 ~ 4, freeze-dried back.Coat 10% glucose RESEARCH OF PYROCARBON on the nano-silicon surface, pattern is shown in Fig. 2 (a) and Fig. 2 (b) before and after coating, taking by weighing 1g nano silica fume, 2g low-level oxidation graphite and 1.67g glucose by the composite Materials Design capacity is dissolved in the appropriate amount of deionized water, 0.15g neopelex is as dispersant, ultrasonic 1h, carry out spray drying after stirring, the gained solid change in the temperature programmed control stove in nitrogen or argon gas atmosphere in 800 ℃ after carrying out the 1 ~ 6h of high temperature place the Si/C composite negative pole material, shown in Fig. 2 (c).
Embodiment 3
Measure dense H
2SO
4Solution, add an amount of sodium nitrate and 10g natural graphite powder in this solution after, be positioned in 0 ℃ of ice bath magnetic agitation 0.5h; Take by weighing 15 ~ 25g potassium bichromate and join slowly in the above-mentioned feed liquid, in 38 ℃, behind the temperature reaction 1.5h, slowly add a large amount of deionized waters and be diluted to about 1L, and the control feed temperature is below 100 ℃; Leave standstill rear filtration, being washed till the pH value with a large amount of absolute ethyl alcohols and deionized water is 3 ~ 4, dry for standby.Taking by weighing nano silica fume, low-level oxidation graphite and phenolic resins by the composite Materials Design capacity is dissolved in an amount of absolute ethyl alcohol, ultrasonic 1h, stir behind the 2h at 80 ℃ of evaporates to dryness, change over to behind the gained solid drying in the temperature programmed control stove in nitrogen or argon gas atmosphere in 800 ℃ after carrying out the 1 ~ 6h of high temperature place the Si/C composite negative pole material.
Claims (10)
1. the preparation method of a lithium ion battery Si/C composite negative pole material is characterized in that, graphite and metallic salt additive are dispersed in the concentrated sulfuric acid solution; Be not higher than 2 ℃ of lower oxidant reactions that add first, again reaction in 32 ~ 38 ℃, the rear deionized water dilute reaction solution of using reacts completely, perhaps be not more than 2 ℃ of lower oxidant reactions that add first, again reaction in 32 ~ 38 ℃, then use the deionized water dilute reaction solution, react 92 ~ 98 ℃ of lower continuation again, continue to spend the ionized water dilute reaction solution and add hydrogen peroxide after reaction is finished; With the reactant liquor Separation of Solid and Liquid of the dilution that obtains at last, separating the solid that obtains, to be washed till pH value with watery hydrochloric acid and deionized water be 3 ~ 4, dry afterwards acquisition low-level oxidation graphite; The low-level oxidation graphite and the silicon source that obtain are dispersed in the solution that is dissolved with carbon source and organic additive, and ultrasonic dispersion obtains suspension after stirring and evenly mixing, and behind the suspension evaporate to dryness, heat-treats under 600 ~ 1000 ℃, and get final product; Silicon source wherein: graphite: the mass ratio of gained RESEARCH OF PYROCARBON is x:y:(1-x-y after the carbon source pyrolysis), 0＜x＜1,0＜y＜1 wherein; The addition in silicon source accounts for 5 ~ 30wt.% of Si/C composite material, the addition of carbon source with heat treatment after the gained RESEARCH OF PYROCARBON count 10 ~ 50wt.% of Si/C composite material.
2. preparation method according to claim 1 is characterized in that, first not being higher than 2 ℃ of lower oxidant reaction 0.3 ~ 0.8h that add, again at 32 ~ 38 ℃ of lower reaction 1 ~ 3h; Or first not being higher than 2 ℃ of lower oxidant reaction 0.3 ~ 0.8h that add, again at 32 ~ 38 ℃ of lower reaction 1 ~ 3h, again at 92 ~ 98 ℃ of lower reaction 1 ~ 3h that continue.
3. preparation method according to claim 1 is characterized in that, described hydrogen peroxide consumption is 0.5 ~ 10 times of graphite quality; The deionized water consumption is 1 ~ 5 times of concentrated sulfuric acid volume.
4. preparation method according to claim 1 is characterized in that, described graphite comprises: one or more in electrographite, native graphite or the graphitized intermediate-phase carbosphere.
5. preparation method according to claim 1 is characterized in that, described silicon source comprises: nano silica fume, silica powder, carbon-coated nano silica flour, carbon coat one or more in the silica powder, and wherein silica powder is SiO
x, 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 the sucrose.
6. preparation method according to claim 1 is characterized in that, described oxidant is one or more in hydrogen peroxide, potassium bichromate or the potassium permanganate.
7. preparation method according to claim 1 is characterized in that, described heat treatment is to process 1 ~ 6h in argon gas or nitrogen environment.
8. preparation method according to claim 1 is characterized in that, the solvent in the described solution that is dissolved with carbon source and organic additive is one or more in deionized water, oxolane, acetone, pyrroles, ethyl acetate or the absolute ethyl alcohol.
9. preparation method according to claim 1 is characterized in that, described Separation of Solid and Liquid is isolated by filtration or centrifugation behind the solution left standstill after will diluting; Suspension evaporate to dryness mode comprises one or more in evaporation curing, vacuumize or the spray drying.
10. preparation method according to claim 1 is characterized in that, described Metal Salts is one or more in sodium nitrate or the 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 the absolute ethyl alcohol.
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Cited By (12)
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| CN104282894A (en) * | 2013-07-08 | 2015-01-14 | 北京化工大学 | Preparation method of porous Si/C composite microsphere |
| CN104852023A (en) * | 2015-04-01 | 2015-08-19 | 廖楚宏 | Carbon composite material and preparation method therefor |
| CN105336953A (en) * | 2015-09-30 | 2016-02-17 | 广西师范大学 | Surface controllable oxidation graphitization mesophase carbon nanosphere negative electrode material and preparation method |
| 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 |
| CN105576241A (en) * | 2016-03-02 | 2016-05-11 | 中国科学院山西煤炭化学研究所 | Preparation method of silicon/carbon composite material applied to high-performance lithium ion battery anodes |
| CN107068996A (en) * | 2017-02-27 | 2017-08-18 | 陕西六元碳晶股份有限公司 | A kind of continuous preparation method of silicon-carbon nitrogen composite |
| 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 |
| WO2018032977A1 (en) * | 2016-08-15 | 2018-02-22 | 福建新峰二维材料科技有限公司 | Manufacturing method of negative-electrode material for lithium-ion battery |
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| 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 |
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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 |
| CN104282894A (en) * | 2013-07-08 | 2015-01-14 | 北京化工大学 | Preparation method of porous Si/C composite microsphere |
| CN104852023A (en) * | 2015-04-01 | 2015-08-19 | 廖楚宏 | Carbon composite material and preparation method therefor |
| CN105336953A (en) * | 2015-09-30 | 2016-02-17 | 广西师范大学 | Surface controllable oxidation graphitization mesophase carbon nanosphere negative electrode material and preparation method |
| 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 |
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| WO2018032977A1 (en) * | 2016-08-15 | 2018-02-22 | 福建新峰二维材料科技有限公司 | Manufacturing method of negative-electrode material for lithium-ion battery |
| CN107068996A (en) * | 2017-02-27 | 2017-08-18 | 陕西六元碳晶股份有限公司 | A kind of continuous preparation method of silicon-carbon nitrogen composite |
| 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 |
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| CN111628153A (en) * | 2020-06-20 | 2020-09-04 | 沈晨 | Novel lithium ion battery cathode material and preparation method thereof |
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