CN103515582A - Preparation method of lithium ion battery silicon-carbon composite cathode material - Google Patents
Preparation method of lithium ion battery silicon-carbon composite cathode material Download PDFInfo
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- CN103515582A CN103515582A CN201310470224.4A CN201310470224A CN103515582A CN 103515582 A CN103515582 A CN 103515582A CN 201310470224 A CN201310470224 A CN 201310470224A CN 103515582 A CN103515582 A CN 103515582A
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a lithium ion battery silicon-carbon composite cathode material. The preparation method is characterized by comprising the following steps: 1), dissolving ethyl orthosilicate in a mixed solution of absolute ethyl alcohol and deionized water, adding organic acid in the solution, regulating the pH value of the solution to 3-5, and marking the solution as a solution A; 2), adding graphite particles in the solution A, stirring the mixture, and marking the mixture as a mixture B; 3), slowly adding ammonia water in the mixture B while stirring by high speed magnetic force, wherein the concentration of the ammonia water is 10-20%, adding a basic catalyst until forming gel; 4), drying gel prepared in the step 3 at 90-110 DEG C; 5), introducing hydrocarbon gas and nitrogen or the mixed gas of nitrogen and argon to the gel material prepared in the step 4 at 600-800 DEG C for 2-6 h, and then introducing high-pure nitrogen or high-pure argon, raising the temperature to 900-1200 DEG C, keeping the temperature for 1-6 h, cooling the mixture, and at last obtaining the silicon-carbon composite cathode material.
Description
Technical field
The invention belongs to field of electrochemical power source, is a kind of method for making of silicon-carbon composite cathode material of lithium ion battery, is specifically related to the method for making of a kind of lithium ion battery silicon/graphite/amorphous carbon composite negative pole material.
Background technology
Lithium ion battery has that operating voltage is high, specific energy is high, fourth does that temperature range is wide, electric discharge steadily, the advantage such as volume is little, quality is light, memory-less effect. at portable electric appts, electric automobile. space technology. the application prospect IIII of wide block up has been shown in the fields such as national defense industry.Along with growing to high power capacity, long-life batteries demand of mobile electronic equipment, people have higher requirement to the performance of lithium ion battery.Negative material, as the key factor that improves lithium ion battery energy and cycle life, has worldwide obtained research widely.
Current commercial lithium ion battery adopts lithium transition-metal oxide/graphite system as active material mostly, although the active material chemical property of this class system is excellent, but it is lower itself to store up lithium ability, particularly the theoretical capacity of carbon negative pole material is only 372mAh/g, the miniaturization development of various portable electric appts and electric automobile be difficult to have been adapted to large capacity, the demand of high power chemical power source.Therefore, studying at present a kind of new performance that the negative active core-shell material of height ratio capacity more improves lithium ion battery that has, to meet the need of market.
Silica-base material theoretical capacity, up to 4200mAh/g, is can meet the negative material most with development prospect of lithium ion battery requirement of new generation at present.But because silicon is in charge and discharge process, violent variation can occur volume, causes motor cycle unstable properties, thereby causes battery failure, and its first irreversible capacity is high, has limited its application as lithium ion battery negative material.
What application was more at present is that employing is adulterated to nano silicon material and coated method is optimized and modification, makes this material more stable, improve to a certain extent the cycle performance of battery, but the problem that nano silicon material is easily reunited still cannot solve.
Summary of the invention
The object of the invention is to address the above problem, a kind of preparation method that can effectively improve silicon/graphite for lithium ion battery/amorphous carbon composite negative pole material of silicon-carbon cathode material cycle performance is provided.
The present invention is a kind of method for making of silicon-carbon composite cathode material of lithium ion battery, it is characterized in that: concrete steps are:
1) select the tetraethoxysilane of institute's expense, be dissolved in the mixed solution of a certain amount of absolute ethyl alcohol and deionized water, add certain amount of organic acid, regulator solution pH value is between 3～5, and this solution is designated as solution A;
2) in solution A, add a certain amount of graphite granule, high speed magnetic stirring 1～3h under 40～60 ℃ of conditions, this mixture is designated as mixture B;
3) under high speed magnetic stirring, in mixture B, slowly add ammoniacal liquor, ammonia concn is 10%～20%; As base catalyst to gel, complete;
4) gel in step 3 is dried at 90～110 ℃, obtains silicon dioxide/graphite composite material;
5) silicon dioxide/graphite composite material obtaining in step 4 is placed in to tube furnace, under 600～800 ℃ of conditions, pass into hydrocarbon gas and nitrogen or nitrogen argon gas gaseous mixture 2～6h, change logical high pure nitrogen or high-purity argon gas, be warming up to 900～1200 ℃, insulation 1～6h, cooling with stove, obtain silicon/graphite/amorphous carbon composite negative pole material;
Wherein: in the solution A described in step 1), the mol ratio of tetraethoxysilane and absolute ethyl alcohol is controlled between 1:1～1:1.5; The mol ratio of tetraethoxysilane and deionized water is controlled between 1:4～1:6; Organic acid is formic acid, acetic acid or oxalic acid;
Step 2) graphite granule described in is natural spherical plumbago, needle coke microballoon or carbonaceous mesophase spherules;
Hydrocarbon gas described in step 5) is ethene, acetylene or propylene.
The negative electrode for lithium ion battery material preparation method that the present invention adopts, is characterized in that adopting two step sol-gel processes to prepare silicon dioxide/graphite composite material.Adopt again chemical vapour deposition technique to prepare silicon/graphite/amorphous carbon composite negative pole material in conjunction with Technology for Heating Processing.The invention has the advantages that preparation method is simple, cost is low, and synthetic material particle size, distributed components, possess good cycle performance, be a kind of desirable lithium ion battery negative material.
Accompanying drawing explanation
Fig. 1 is silicon/graphite/amorphous carbon composite negative pole material first charge-discharge curve chart of embodiment 1.
Fig. 2 is silicon/graphite/amorphous carbon composite negative pole material circulation volume figure of embodiment 1.
Specific embodiment
Embodiment 1
Measure 45ml tetraethoxysilane and be dissolved in 12ml absolute ethyl alcohol, then add 15ml deionized water, the formation clear solution that stirs, drips oxalic acid, regulator solution pH value to 4; Add 22.4g MCMB (D50 is 12um), high speed magnetic stirring 2.5h under 50 ℃ of conditions, slowly adding concentration is that 10% ammoniacal liquor to gel completes; Gel is placed in to the dry silicon dioxide/graphite composite material that obtains of 105 ℃ of baking ovens.Silicon dioxide/the graphite composite material obtaining is placed in to tube furnace, under 750 ℃ of conditions, passes into propylene gas after argon gas gaseous mixture (5%vol propylene) 3.5h, change logical argon gas, be warming up to 1100 ℃, insulation 5h, cooling with stove, obtain silicon/graphite/amorphous carbon composite negative pole material.The composite material making, acetylene black, PVdF are made to slurry according to mass ratio 80:10:10, evenly be coated on (14um) on Copper Foil, after oven dry, be stamped into circular electrode pole piece, take lithium metal as to electrode, 1mol/LLiPF6/DMC+DEC+EC(volume ratio is 1:1:1) be electrolyte, Celgard2400 is barrier film, is assembled into button cell.Battery is carried out to charge-discharge test, and charging/discharging voltage scope is 0.01V～2.5V, and measured result is, 0.1C first discharge specific capacity and charge ratio capacity are respectively 1034.5mAh/g and 809.6mAh/g, and the material specific capacity after 50 times that circulates is 687.4mAh/g.
Embodiment 2
Measure 45ml tetraethoxysilane and be dissolved in 12ml absolute ethyl alcohol, then add 15ml deionized water, the formation clear solution that stirs, drips oxalic acid, regulator solution pH value to 4; Add 13.1g native graphite (D50 is 8um), high speed magnetic stirring 2h under 53 ℃ of conditions, slowly adding concentration is that 10% ammoniacal liquor to gel completes; Gel is placed in to the dry silicon dioxide/graphite composite material that obtains of 105 ℃ of baking ovens.Silicon dioxide/the graphite composite material obtaining is placed in to tube furnace, under 750 ℃ of conditions, passes into propylene gas after argon gas gaseous mixture (5%vol propylene) 3.5h, change logical argon gas, be warming up to 1150 ℃, insulation 4h, cooling with stove, obtain silicon/graphite/amorphous carbon composite negative pole material.The composite material making, acetylene black, PVdF are made to slurry according to mass ratio 80:10:10, evenly be coated on (14um) on Copper Foil, after oven dry, be stamped into circular electrode pole piece, take lithium metal as to electrode, 1mol/L LiPF6/DMC+DEC+EC(volume ratio is 1:1:1) be electrolyte, Celgard2400 is barrier film, is assembled into button cell.Battery is carried out to charge-discharge test, and charging/discharging voltage scope is 0.01V～2.5V, and measured result is, 0.1C first discharge specific capacity and charge ratio capacity are respectively 1290.9mAh/g and 986.7mAh/g, and the material specific capacity after 50 times that circulates is 704.3mAh/g.
Embodiment 3
Measure 45ml tetraethoxysilane and be dissolved in 12ml absolute ethyl alcohol, then add 15ml deionized water, the formation clear solution that stirs, drips oxalic acid, regulator solution pH value to 4; Add 8.4g MCMB (D50 is 8um), high speed magnetic stirring 1h under 55 ℃ of conditions, slowly adding concentration is that 10% ammoniacal liquor to gel completes; Gel is placed in to the dry silicon dioxide/graphite composite material that obtains of 105 ℃ of baking ovens.Silicon dioxide/the graphite composite material obtaining is placed in to tube furnace, under 750 ℃ of conditions, passes into propylene gas after argon gas gaseous mixture (5%vol propylene) 6h, change logical argon gas, be warming up to 1150 ℃, insulation 6h, cooling with stove, obtain silicon/graphite/amorphous carbon composite negative pole material.The composite material making, acetylene black, PVdF are made to slurry according to mass ratio 80:10:10, evenly be coated on (14um) on Copper Foil, after oven dry, be stamped into circular electrode pole piece, take lithium metal as to electrode, 1mol/L LiPF6/DMC+DEC+EC(volume ratio is 1:1:1) be electrolyte, Celgard2400 is barrier film, is assembled into button cell.Battery is carried out to charge-discharge test, and charging/discharging voltage scope is 0.01V～2.5V, and measured result is, 0.1C first discharge specific capacity and charge ratio capacity are respectively 1384.5mAh/g and 1026.6mAh/g, and the material specific capacity after 50 times that circulates is 657.3mAh/g.
Claims (1)
1. a method for making for silicon-carbon composite cathode material of lithium ion battery, is characterized in that: concrete steps are:
1) select the tetraethoxysilane of institute's expense, be dissolved in the mixed solution of a certain amount of absolute ethyl alcohol and deionized water, add certain amount of organic acid, regulator solution pH value is between 3～5, and this solution is designated as solution A;
2) in solution A, add a certain amount of graphite granule, high speed magnetic stirring 1～3h under 40～60 ℃ of conditions, this mixture is designated as mixture B;
3) under high speed magnetic stirring, in mixture B, slowly add ammoniacal liquor, ammonia concn is 10%～20%; As base catalyst to gel, complete;
4) gel in step 3 is dried at 90～110 ℃, obtains silicon dioxide/graphite composite material;
5) silicon dioxide/graphite composite material obtaining in step 4 is placed in to tube furnace, under 600～800 ℃ of conditions, pass into hydrocarbon gas and nitrogen or nitrogen argon gas gaseous mixture 2～6h, change logical high pure nitrogen or high-purity argon gas, be warming up to 900～1200 ℃, insulation 1～6h, cooling with stove, obtain silicon/graphite/amorphous carbon composite negative pole material;
Wherein: in the solution A described in step 1), the mol ratio of tetraethoxysilane and absolute ethyl alcohol is controlled between 1:1～1:1.5; The mol ratio of tetraethoxysilane and deionized water is controlled between 1:4～1:6; Organic acid is formic acid, acetic acid or oxalic acid;
Step 2) graphite granule described in is natural spherical plumbago, needle coke microballoon or carbonaceous mesophase spherules;
Hydrocarbon gas described in step 5) is ethene, acetylene or propylene.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105185937A (en) * | 2015-10-23 | 2015-12-23 | 旭成（福建）科技股份有限公司 | Non-woven fabric ceramic diaphragm for lithium ion battery and preparation method of non-woven fabric ceramic diaphragm |
| CN106058276A (en) * | 2016-07-11 | 2016-10-26 | 华南理工大学 | Preparation method of silica-modified multi-spherical-cavity carbon material and application of carbon material to fuel cell membrane electrode |
| CN106299322A (en) * | 2016-11-24 | 2017-01-04 | 杭州启澄科技有限公司 | A kind of high-capacity lithium ion cell electrode composite nano materials and preparation method thereof |
| CN106784717A (en) * | 2016-12-29 | 2017-05-31 | 湖北宇电能源科技股份有限公司 | A kind of preparation method of nano silicon coated graphite negative material |
| CN107068987A (en) * | 2016-12-16 | 2017-08-18 | 深圳市沃特玛电池有限公司 | The preparation method and lithium ion battery of a kind of anode plate for lithium ionic cell |
| CN107851781A (en) * | 2015-06-02 | 2018-03-27 | 富士硅化学株式会社 | Negative electrode active material composition, negative pole, the manufacture method of rechargeable nonaqueous electrolytic battery and negative electrode active material composition |
| CN108258214A (en) * | 2018-01-08 | 2018-07-06 | 北京科技大学 | A kind of preparation method of lithium ion battery negative material silicon@graphene/carbons |
| CN112635731A (en) * | 2020-12-17 | 2021-04-09 | 浙江锂宸新材料科技有限公司 | Preparation method of composite nano-silicon negative electrode material based on conductive carbon aerogel and product thereof |
| CN113241427A (en) * | 2021-04-14 | 2021-08-10 | 合肥国轩高科动力能源有限公司 | High-performance silicon-carbon negative electrode material and preparation method thereof |
| CN113735108A (en) * | 2021-09-08 | 2021-12-03 | 四川星耀新能源科技有限公司 | Porous graphite silicon carbon composite material and preparation method and application thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107851781A (en) * | 2015-06-02 | 2018-03-27 | 富士硅化学株式会社 | Negative electrode active material composition, negative pole, the manufacture method of rechargeable nonaqueous electrolytic battery and negative electrode active material composition |
| CN105185937A (en) * | 2015-10-23 | 2015-12-23 | 旭成（福建）科技股份有限公司 | Non-woven fabric ceramic diaphragm for lithium ion battery and preparation method of non-woven fabric ceramic diaphragm |
| CN106058276A (en) * | 2016-07-11 | 2016-10-26 | 华南理工大学 | Preparation method of silica-modified multi-spherical-cavity carbon material and application of carbon material to fuel cell membrane electrode |
| CN106058276B (en) * | 2016-07-11 | 2018-07-20 | 华南理工大学 | A kind of preparation method of silicon dioxide modified more spherical cavity carbon materials and its application in fuel cell membrane electrode |
| CN106299322A (en) * | 2016-11-24 | 2017-01-04 | 杭州启澄科技有限公司 | A kind of high-capacity lithium ion cell electrode composite nano materials and preparation method thereof |
| CN107068987B (en) * | 2016-12-16 | 2018-07-24 | 深圳市沃特玛电池有限公司 | A kind of production method and lithium ion battery of anode plate for lithium ionic cell |
| CN107068987A (en) * | 2016-12-16 | 2017-08-18 | 深圳市沃特玛电池有限公司 | The preparation method and lithium ion battery of a kind of anode plate for lithium ionic cell |
| CN106784717A (en) * | 2016-12-29 | 2017-05-31 | 湖北宇电能源科技股份有限公司 | A kind of preparation method of nano silicon coated graphite negative material |
| CN108258214A (en) * | 2018-01-08 | 2018-07-06 | 北京科技大学 | A kind of preparation method of lithium ion battery negative material silicon@graphene/carbons |
| CN112635731A (en) * | 2020-12-17 | 2021-04-09 | 浙江锂宸新材料科技有限公司 | Preparation method of composite nano-silicon negative electrode material based on conductive carbon aerogel and product thereof |
| CN113241427A (en) * | 2021-04-14 | 2021-08-10 | 合肥国轩高科动力能源有限公司 | High-performance silicon-carbon negative electrode material and preparation method thereof |
| CN113735108A (en) * | 2021-09-08 | 2021-12-03 | 四川星耀新能源科技有限公司 | Porous graphite silicon carbon composite material and preparation method and application thereof |
| CN113735108B (en) * | 2021-09-08 | 2024-03-12 | 四川星耀新能源科技有限公司 | Porous graphite silicon-carbon composite material and preparation method and application thereof |
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