CN102569759A - Process for preparing materials of silicon-porous carbon negative electrodes of lithium-ion batteries - Google Patents
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- CN102569759A CN102569759A CN2012100018487A CN201210001848A CN102569759A CN 102569759 A CN102569759 A CN 102569759A CN 2012100018487 A CN2012100018487 A CN 2012100018487A CN 201210001848 A CN201210001848 A CN 201210001848A CN 102569759 A CN102569759 A CN 102569759A
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Abstract
The invention relates to a process for preparing materials of silicon-porous carbon negative electrodes of lithium-ion batteries, which belongs to the technical field of preparing processes of chemical engineering electrode materials. The process comprises the steps of uniformly mixing magnesium powder or aluminum powder with silica, adding porous carbon, transferring obtained powder to a tube furnace, introducing inert gases, taking out products after a heating reaction is completed and the temperature of the tube furnace is cooled to the room temperature, adding the products into hydrochloric acid, and washing and filtering the products with deionized water till the pH of filtrate is neutral; and then adding the products into a hydrofluoric acid solution, washing and filtering with deionized water till the pH of filtrate is neutral, and drying filter cakes to obtain silicon-porous carbon composite materials of negative electrodes having nano-porous structures. The process is easy and practical, the controllability of preparation parameters is high, obtained products have nano-porous structures which provide a certain buffer space for volumetric expansion of silicon, simultaneously, the introduction of carbon enhances the electrical conductivity of materials, and the products have a high charging and discharging capacity and good cycling performances when serving as materials of negative electrodes of lithium-ion batteries.
Description
Technical field
The present invention relates to a kind of method for preparing lithium ion battery silicon-porous carbon negative material, belong to chemical industry electrode material manufacturing process technology field.
Background technology
Lithium ion battery is since successfully developing the beginning of the nineties in last century; Just receive much attention with unique advantages such as its specific energy are high, operating voltage is high, temperature limit is wide, self-discharge rate is low, have extended cycle life, pollution-free, and extensive use in small portable electronic products such as mobile phone, digital camera, notebook computer.In recent years; For reply auto industry fast development bring such as the sharply negative effect such as consumptions of environmental pollution, petroleum resources, countries such as the U.S., Japan, China are all in electric automobile EV that actively develops the employing clean energy resource and the R&D work of PHEV HEV.And lithium ion battery is as the topmost candidate's electrical source of power of following electric automobile; Have characteristics with low cost, excellent performance; Become the main research focus in international electrokinetic cell field, wherein the exploitation as the function admirable electrode material of one of key factor that improves the lithium ion battery performance is the emphasis of research always.
At present; The main negative material of in lithium ion battery, using is traditional graphite-like material with carbon element; Material with carbon element itself has in the charge and discharge process advantages such as voltage is stable, good cycle; But Along with people's is to the pursuit of high capacity characteristics, and material with carbon element has demonstrated certain limitation owing to theoretical capacity is merely 372mAh/g.In recent years, some non-carbon negative pole materials had become one of focus of lithium ion battery negative material research owing to the more excellent security ability that has high specific capacity and removal lithium embedded current potential and bring thus.The silicon based material promptly is a kind of like this high power capacity negative material; Its highest theoretical value specific capacity can reach 4200mAh/g, and low with the electrolyte reactivity, and this material is abundant at natural content; Cost of material is cheap, has good prospect and potentiality as the new type lithium ion battery negative material.But because there is serious bulk effect in silicon under height removal lithium embedded condition, the material efflorescence is serious, causes its relatively poor cyclical stability, and capacity attenuation is very fast.Recent study personnel have carried out a series of study on the modification to the silicon-based anode material, comprise nanometerization to silicon, coat silicon and preparation silicon alloy composite material or the like with carbon-coating, but the cycle performance of silicium cathode material is not improved at all.The present invention selects the complex carrier of porous carbon as silicon; Utilize porous carbon materials structure flourishing hole and good electrical conductivity; Through thermal reduction elemental silicon is deposited in the pore passage structure of porous carbon; Prepare silicon-porous carbon composite material, improved the cyclical stability of silicium cathode material, have certain popularization value.
Summary of the invention
The objective of the invention is in order to solve serious, the poorly conductive of existing lithium ion battery silicon negative material efflorescence; Capacity attenuation reaches the problem of cyclical stability difference soon; To improve the chemical property of lithium ion battery silicon negative material, a kind of method for preparing lithium ion battery silicon-porous carbon negative material is provided.
The objective of the invention is to realize through following technical scheme.
A kind of method for preparing lithium ion battery silicon-porous carbon negative material of the present invention, concrete steps are:
1) be that 1～10: 1 ground and mixed is even in molar ratio with metallic reducing agent and SiO 2 powder;
2) porous carbon is added in the mixed-powder that step 1) obtains, wherein porous carbon and silicon dioxide quality ratio are 1: 0.2～20, grind to make three kinds of powder even;
3) with step 2) powder that obtains moves in the tube furnace, feeds inert gas, and heating reacts, and the reaction time is 2～24h;
4) after reaction finishes, treat that the tube furnace temperature is cooled to room temperature, take out product and join in the hydrochloric acid that concentration is 0.1～2mol/L, soak 4～24h, be neutral with deionized water wash, suction filtration to the pH that filtrates again;
5) it is in 10%～40% the hydrofluoric acid solution that the product that step 4) is obtained joins mass fraction; Soak time is 10min～3h; Be neutral with deionized water wash, suction filtration to the pH that filtrates,, obtain having the silicon-porous carbon composite negative pole material of nano-porous structure the filter cake in vacuum oven dry.
Above-mentioned steps 1) metallic reducing agent is magnesium powder or aluminium powder in;
Above-mentioned steps 3) heating-up temperature is 500～1000 ℃ in, and the rate of heat addition is 5 ℃/min; Inert gas is argon gas or nitrogen.
Beneficial effect
It is of the present invention that preparation is simple; The preparation parameter controllability is strong; Silicon-porous carbon the composite material of preparation gained has nano-porous structure; For the volumetric expansion of silicon provides certain cushion space, the introducing of carbon has simultaneously strengthened the conductivity of material, shows high charging and discharging capacity and excellent cycle performance as lithium ion battery negative material.
Description of drawings
Fig. 1 is the SEM shape appearance figure of the silicon-porous carbon negative material of embodiment preparation;
Fig. 2 is silicon-porous carbon negative material specific capacity and enclosed pasture efficiency curves figure when under 100mA/g, discharging and recharging.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is elaborated
Embodiment
A kind of method for preparing lithium ion battery silicon-porous carbon negative material, concrete steps are:
1) it is mixed 1g magnesium powder and 1g SiO 2 powder abundant grinding in mortar;
2) (mesoporous, aperture is 30～50nm) to join in the mixed-powder that step 1) obtains, and fully grinds to make three kinds of powder even with the 0.94g porous carbon;
3) above three kinds of mixed-powders are moved in the tube furnace, feed argon gas, heating, heating-up temperature is 650 ℃, and the rate of heat addition is 5 ℃/min, and the reaction time is 6h;
4) after reaction is accomplished, treat that the tube furnace temperature is cooled to room temperature, take out product and join in the hydrochloric acid that concentration is 0.5mol/L, soak 6h, again with deionized water wash, suction filtration repeatedly 5 rear filtrate pH be neutrality;
5) it is in 20% the hydrofluoric acid solution that the product that step 4) is obtained joins mass fraction; Soak time is 2h; With deionized water wash, suction filtration repeatedly 6 rear filtrate pH be neutral; With 120 ℃ of bakings of suction filtration product vacuum 12h, obtain having the silicon-porous carbon composite negative pole material of nano-porous structure, its SEM shape appearance figure is as shown in Figure 1.
The silicon that obtains-porous carbon composite negative pole material is applied to carry out charging and discharging capacity and cycle performance test behind the lithium ion battery negative material: silicon-porous carbon negative material and conductive agent, binding agent are mixed and made into electrode slice as work electrode; Lithium metal is to electrode, the LiF of 1mol/L
6/ EC-DMC (volume ratio 1: 1) is an electrolyte, in the argon gas atmosphere glove box, is assembled into simulated battery.Simulated battery is carried out charge-discharge test, and voltage range is 0.01～2V (vs.Li
+/ Li), current density is 100mA/g.
Test result: specific capacity and enclosed pasture efficiency curves were as shown in Figure 2 when silicon-porous carbon negative material discharged and recharged under 100mA/g; Its discharge first (embedding lithium) specific capacity and charging (taking off lithium) specific capacity are respectively 2185.9mAh/g, 1220.9mAh/g, 30 week of circulation back its discharge (embedding lithium) specific capacities and charging (taking off lithium) specific capacity be respectively 672.3mAh/g, 653.9mAh/g.
Claims (3)
1. method for preparing lithium ion battery silicon-porous carbon negative material is characterized in that concrete steps are:
1) be that 1～10: 1 ground and mixed is even in molar ratio with metallic reducing agent and SiO 2 powder;
2) porous carbon is added in the mixed-powder that step 1) obtains, wherein porous carbon and silicon dioxide quality ratio are 1: 0.2～20, grind to make three kinds of powder even;
3) with step 2) powder that obtains moves in the tube furnace, feeds inert gas, and heating reacts, and the reaction time is 2～24h;
4) after reaction finishes, treat that the tube furnace temperature is cooled to room temperature, take out product and join in the hydrochloric acid that concentration is 0.1～2mol/L, soak 4～24h, be neutral with deionized water wash, suction filtration to the pH that filtrates again;
5) it is in 10%～40% the hydrofluoric acid solution that the product that step 4) is obtained joins mass fraction; Soak time is 10min～3h; Be neutral with deionized water wash, suction filtration to the pH that filtrates,, obtain having the silicon-porous carbon composite negative pole material of nano-porous structure the filter cake in vacuum oven dry.
2. a kind of method for preparing lithium ion battery silicon-porous carbon negative material according to claim 1, it is characterized in that: the metallic reducing agent in the step 1) is magnesium powder or aluminium powder.
3. a kind of method for preparing lithium ion battery silicon-porous carbon negative material according to claim 1, it is characterized in that: heating-up temperature is 500～1000 ℃ in the step 3), the rate of heat addition is 5 ℃/min; Inert gas is argon gas or nitrogen.
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102738460A (en) * | 2012-07-17 | 2012-10-17 | 中国电子科技集团公司第十八研究所 | Surface passivating treatment method of spinel type manganese-based positive pole material |
| CN102820451A (en) * | 2012-07-23 | 2012-12-12 | 深圳市海太阳实业有限公司 | Negative electrode pole piece and preparation method thereof, and lithium ion battery and preparation method thereof |
| CN102983313A (en) * | 2012-12-05 | 2013-03-20 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof, and lithium ion battery |
| 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 |
| CN103779544A (en) * | 2014-01-07 | 2014-05-07 | 浙江大学 | Preparation method of porous silicon/carbon composite material |
| CN103985846A (en) * | 2014-05-30 | 2014-08-13 | 西安交通大学 | Carbon-loaded silica nanoparticle structure as well as preparation method and application thereof |
| CN104332621A (en) * | 2014-09-27 | 2015-02-04 | 奇瑞汽车股份有限公司 | Method for preparing hollow nano silicon microsphere through metal thermal reduction and lithium ion battery |
| CN105489891A (en) * | 2015-12-21 | 2016-04-13 | 宁波高新区锦众信息科技有限公司 | Preparation method for high-capacity silicon-based negative electrode material for lithium ion battery |
| CN106549149A (en) * | 2016-10-28 | 2017-03-29 | 浙江天能能源科技股份有限公司 | A kind of preparation method and application of Si-C composite material |
| CN107074560A (en) * | 2015-10-29 | 2017-08-18 | 瓦克化学股份公司 | The method for being used to produce silicon by magnesiothermic reduction |
| CN107195871A (en) * | 2017-04-06 | 2017-09-22 | 中国计量大学 | A kind of preparation method that SiOx/C negative materials are synthesized by carrier low temperature of carbon material |
| CN109659549A (en) * | 2019-01-14 | 2019-04-19 | 北京科技大学 | Lithium battery multilevel structure silicon-porous carbon compound cathode materials preparation method |
| CN109659529A (en) * | 2018-12-17 | 2019-04-19 | 潍坊汇成新材料科技有限公司 | A kind of preparation process of silicon-carbon cathode material |
| CN110233251A (en) * | 2019-06-20 | 2019-09-13 | 浙江工业大学 | A kind of preparation method and applications of porous silicon/carbon composite material |
| CN111048764A (en) * | 2019-12-23 | 2020-04-21 | 北京理工大学重庆创新中心 | Silicon-carbon composite material and preparation method and application thereof |
| CN113666354A (en) * | 2020-05-13 | 2021-11-19 | 北京小米移动软件有限公司 | Preparation method of silicon-carbon composite material, silicon negative electrode piece and battery |
| CN115298352A (en) * | 2022-06-24 | 2022-11-04 | 上海杉杉科技有限公司 | Silicon-based lithium storage material and preparation method thereof |
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| CN102208634A (en) * | 2011-05-06 | 2011-10-05 | 北京科技大学 | Porous silicon/carbon composite material and preparation method thereof |
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| CN101609891A (en) * | 2007-07-27 | 2009-12-23 | 三星Sdi株式会社 | Si/C compound, negative active core-shell material and comprise its lithium battery |
| CN102208634A (en) * | 2011-05-06 | 2011-10-05 | 北京科技大学 | Porous silicon/carbon composite material and preparation method thereof |
| CN102208636A (en) * | 2011-05-12 | 2011-10-05 | 北京科技大学 | Method for preparing porous silicon/carbon composite material by using diatomite as raw material and application |
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| CN102738460A (en) * | 2012-07-17 | 2012-10-17 | 中国电子科技集团公司第十八研究所 | Surface passivating treatment method of spinel type manganese-based positive pole material |
| CN102820451A (en) * | 2012-07-23 | 2012-12-12 | 深圳市海太阳实业有限公司 | Negative electrode pole piece and preparation method thereof, and lithium ion battery and preparation method thereof |
| CN102983313A (en) * | 2012-12-05 | 2013-03-20 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof, and lithium ion battery |
| CN103022446B (en) * | 2012-12-19 | 2015-10-07 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of lithium ion battery silicon oxide/carbon negative material and preparation method thereof |
| 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 |
| CN103779544A (en) * | 2014-01-07 | 2014-05-07 | 浙江大学 | Preparation method of porous silicon/carbon composite material |
| CN103779544B (en) * | 2014-01-07 | 2016-04-20 | 浙江大学 | A kind of preparation method of porous silicon/carbon composite material |
| CN103985846B (en) * | 2014-05-30 | 2016-08-17 | 西安交通大学 | A kind of silicon nanoparticle structure of carbon load and its preparation method and application |
| CN103985846A (en) * | 2014-05-30 | 2014-08-13 | 西安交通大学 | Carbon-loaded silica nanoparticle structure as well as preparation method and application thereof |
| CN104332621A (en) * | 2014-09-27 | 2015-02-04 | 奇瑞汽车股份有限公司 | Method for preparing hollow nano silicon microsphere through metal thermal reduction and lithium ion battery |
| CN107074560B (en) * | 2015-10-29 | 2019-04-12 | 瓦克化学股份公司 | The method for being used to produce silicon by magnesiothermic reduction |
| CN107074560A (en) * | 2015-10-29 | 2017-08-18 | 瓦克化学股份公司 | The method for being used to produce silicon by magnesiothermic reduction |
| CN105489891A (en) * | 2015-12-21 | 2016-04-13 | 宁波高新区锦众信息科技有限公司 | Preparation method for high-capacity silicon-based negative electrode material for lithium ion battery |
| CN106549149A (en) * | 2016-10-28 | 2017-03-29 | 浙江天能能源科技股份有限公司 | A kind of preparation method and application of Si-C composite material |
| CN107195871A (en) * | 2017-04-06 | 2017-09-22 | 中国计量大学 | A kind of preparation method that SiOx/C negative materials are synthesized by carrier low temperature of carbon material |
| CN109659529A (en) * | 2018-12-17 | 2019-04-19 | 潍坊汇成新材料科技有限公司 | A kind of preparation process of silicon-carbon cathode material |
| CN109659549A (en) * | 2019-01-14 | 2019-04-19 | 北京科技大学 | Lithium battery multilevel structure silicon-porous carbon compound cathode materials preparation method |
| CN109659549B (en) * | 2019-01-14 | 2021-02-12 | 北京科技大学 | Preparation method of multi-stage structure silicon-porous carbon composite negative electrode material for lithium battery |
| CN110233251A (en) * | 2019-06-20 | 2019-09-13 | 浙江工业大学 | A kind of preparation method and applications of porous silicon/carbon composite material |
| CN111048764A (en) * | 2019-12-23 | 2020-04-21 | 北京理工大学重庆创新中心 | Silicon-carbon composite material and preparation method and application thereof |
| CN113666354A (en) * | 2020-05-13 | 2021-11-19 | 北京小米移动软件有限公司 | Preparation method of silicon-carbon composite material, silicon negative electrode piece and battery |
| CN113666354B (en) * | 2020-05-13 | 2023-04-04 | 北京小米移动软件有限公司 | Preparation method of silicon-carbon composite material, silicon negative electrode piece and battery |
| CN115298352A (en) * | 2022-06-24 | 2022-11-04 | 上海杉杉科技有限公司 | Silicon-based lithium storage material and preparation method thereof |
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