CN102569759B - Process for preparing materials of silicon-porous carbon negative electrodes of lithium-ion batteries - Google Patents
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- CN102569759B CN102569759B CN201210001848.7A CN201210001848A CN102569759B CN 102569759 B CN102569759 B CN 102569759B CN 201210001848 A CN201210001848 A CN 201210001848A CN 102569759 B CN102569759 B CN 102569759B
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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 materials of silicon-porous carbon negative electrodes of lithium-ion batteries, belong to chemical industry electrode material manufacturing process technology field.
Background technology
Lithium ion battery is since beginning of the nineties in last century develop, just high with its specific energy, operating voltage is high, temperature limit is wide, self-discharge rate is low, have extended cycle life, the unique advantage such as pollution-free and receiving much attention, and extensive use in the small portable electronic products such as mobile phone, digital camera, notebook computer.In recent years, for reply auto industry fast development bring such as negative effects such as environmental pollution, petroleum resources sharply consume, the countries such as the U.S., Japan, China are all in the electric automobile EV that actively develops the employing clean energy resource and the R&D work of hybrid electric vehicle HEV.And lithium ion battery is as the topmost candidate's electrical source of power of following electric automobile, there are characteristics with low cost, excellent performance, become the main study hotspot in international electrokinetic cell field, wherein the exploitation as the function admirable electrode material of one of key factor that improves performance of lithium ion battery is the emphasis of research always.
At present, the main negative material of applying in lithium ion battery is traditional graphite-like material with carbon element, material with carbon element itself has the advantage such as voltage stabilization, good cycle in charge and discharge process, but, along with the pursuit of people to high capacity characteristics, material with carbon element is because theoretical capacity has only demonstrated certain limitation for 372mAh/g.In recent years, some non-carbon negative pole materials, due to the more excellent security performance that has high specific capacity and removal lithium embedded current potential and bring thus, had become one of focus of lithium ion battery negative material research.The silicon based material is a kind of like this high power capacity negative material, its the highest theoretical value specific capacity can reach 4200mAh/g, and low with the electrolyte reactivity, and this material is at natural rich content, cost of material is cheap, as Novel cathode material for lithium ion battery, has good prospect and potentiality.But because there is serious bulk effect in silicon under height removal lithium embedded condition, the material efflorescence is serious, causes its poor cyclical stability, and capacity attenuation is very fast.Recent study personnel have carried out a series of study on the modification to silicon based anode material, comprise nanometer to silicon, with the carbon-coating coated Si and prepare silicon alloy composite material etc., but the cycle performance of silicium cathode material is not fundamentally improved.The present invention selects the complex carrier of porous carbon as silicon, utilize the hole of porous carbon materials structure prosperity and good conductivity, by thermal reduction, elemental silicon is deposited in the pore passage structure of porous carbon, prepare silicon-porous carbon composite material, improve the cyclical stability of silicium cathode material, there is certain promotional value.
Summary of the invention
The objective of the invention is that existing lithium ion battery silicon negative material efflorescence is serious, poorly conductive in order to solve, capacity attenuation reaches the poor problem of cyclical stability soon, to improve the chemical property of lithium ion battery silicon negative material, provide a kind of method for preparing materials of silicon-porous carbon negative electrodes of lithium-ion batteries.
The objective of the invention is to be achieved through the following technical solutions.
A kind of method for preparing materials of silicon-porous carbon negative electrodes of lithium-ion batteries of the present invention, concrete steps are:
1) by metallic reducing agent and SiO 2 powder, be that 1～10: 1 ground and mixed is even in molar ratio;
2) porous carbon being added to step 1) in the mixed-powder that obtains, wherein porous carbon and silicon dioxide quality ratio are 1: 0.2～20, grind three kinds of powder are mixed;
3) by step 2) powder that obtains moves in tube furnace, passes into 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, then be neutral with deionized water washing, suction filtration to filtrate pH;
5) by step 4) product that obtains joins in the hydrofluoric acid solution that mass fraction is 10%～40%, soak time is 10min～3h, be neutral with deionized water washing, suction filtration to filtrate pH, by the filter cake vacuum drying, obtain having the silicon of nano-porous structure-porous carbon composite negative pole material.
Above-mentioned steps 1) in, metallic reducing agent is magnesium powder or aluminium powder;
Above-mentioned steps 3) in, heating-up temperature is 500～1000 ℃, 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, prepare the silicon of gained-porous carbon composite material and there is nano-porous structure, for the volumetric expansion of silicon provides certain cushion space, the introducing of carbon has simultaneously strengthened the conductivity of material, as lithium ion battery negative material, shows high charging and discharging capacity and good cycle performance.
The accompanying drawing explanation
The SEM shape appearance figure that Fig. 1 is the silicon for preparing of embodiment-porous carbon negative material;
Fig. 2 is silicon-porous carbon negative material specific capacity and enclosed pasture efficiency curves figure while discharging and recharging under 100mA/g.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is elaborated
Embodiment
A kind of method for preparing materials of silicon-porous carbon negative electrodes of lithium-ion batteries, concrete steps are:
1) 1g magnesium powder and 1g SiO 2 powder are fully ground it is mixed in mortar;
2) 0.94g porous carbon (mesoporous, aperture is 30～50nm) is joined to step 1) in the mixed-powder that obtains, fully grind three kinds of powder are mixed;
3) above three kinds of mixed-powders are moved in tube furnace, pass into 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 having reacted, 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, then with deionized water washing, suction filtration repeatedly after 5 times filtrate pH be neutral;
5) by step 4) product that obtains joins in the hydrofluoric acid solution that mass fraction is 20%, soak time is 2h, with deionized water washing, suction filtration repeatedly after 6 times filtrate pH be neutral, 120 ℃, suction filtration product vacuum is dried to 12h, obtain having the silicon of nano-porous structure-porous carbon composite negative pole material, its SEM shape appearance figure as shown in Figure 1.
Carry out charging and discharging capacity and cycle performance test after the silicon that obtains-porous carbon composite negative pole material is applied to 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 electrolyte, in the argon gas atmosphere glove box, is assembled into simulated battery.Simulated battery is carried out to charge-discharge test, and voltage range is 0.01～2V (vs.Li
+/ Li), current density is 100mA/g.
Test result: when silicon-porous carbon negative material discharges and recharges under 100mA/g, specific capacity and enclosed pasture efficiency curves are as shown in Figure 2, its discharge first (embedding lithium) specific capacity and charging (de-lithium) specific capacity is respectively 2185.9mAh/g, 1220.9mAh/g, and after circulating 30 weeks, its electric discharge (embedding lithium) specific capacity and charging (taking off lithium) specific capacity is respectively 672.3mAh/g, 653.9mAh/g.
Claims (2)
1. a method for preparing materials of silicon-porous carbon negative electrodes of lithium-ion batteries is characterized in that concrete steps are:
1) by metallic reducing agent and SiO 2 powder, be that 1～10:1 ground and mixed is even in molar ratio;
2), in the mixed-powder that adds step 1) to obtain porous carbon, wherein porous carbon and silicon dioxide quality, than being 1:0.2～20, are ground three kinds of powder are mixed;
3) by step 2) powder that obtains moves in tube furnace, passes into 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, then be neutral with deionized water washing, suction filtration to filtrate pH;
5) product step 4) obtained joins in the hydrofluoric acid solution that mass fraction is 10%～40%, soak time is 10min～3h, be neutral with deionized water washing, suction filtration to filtrate pH, by the filter cake vacuum drying, obtain having the silicon of nano-porous structure-porous carbon composite negative pole material;
In step 3), heating-up temperature is 500～1000 ℃, and the rate of heat addition is 5 ℃/min; Inert gas is argon gas or nitrogen.
2. a kind of method for preparing materials of silicon-porous carbon negative electrodes of lithium-ion batteries according to claim 1, it is characterized in that: the metallic reducing agent in step 1) is magnesium powder or aluminium powder.
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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 |
| CN102983313B (en) * | 2012-12-05 | 2016-01-27 | 奇瑞汽车股份有限公司 | Si-C composite material and preparation method thereof, 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 |
| 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 |
| 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 |
| DE102015221226A1 (en) * | 2015-10-29 | 2017-05-04 | Wacker Chemie Ag | Process for the production of silicon |
| 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 |
| 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 |
| 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 |
| CN115298352B (en) * | 2022-06-24 | 2024-05-03 | 上海杉杉科技有限公司 | Silicon-based lithium storage material and preparation method thereof |
| CN117438558B (en) * | 2023-10-23 | 2024-05-24 | 柔电（武汉）科技有限公司 | Silicon-carbon negative electrode and preparation method thereof |
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