CN100379059C - Composite cathode material of silicon/carbon/graphite in lithium ion batteries, and preparation method - Google Patents
Composite cathode material of silicon/carbon/graphite in lithium ion batteries, and preparation method Download PDFInfo
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- CN100379059C CN100379059C CNB2005100307858A CN200510030785A CN100379059C CN 100379059 C CN100379059 C CN 100379059C CN B2005100307858 A CNB2005100307858 A CN B2005100307858A CN 200510030785 A CN200510030785 A CN 200510030785A CN 100379059 C CN100379059 C CN 100379059C
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Abstract
The present invention relates to a silicon /carbon /graphite composite negative electrode material of a lithium ion battery and a preparation method thereof, which belongs to the field of electrochemical power source. The composite negative electrode material is composed of elemental silicon, graphite particles and amorphous carbon, and the method comprises the following steps: firstly, silicon powders and the graphite are mixed for ball milling, materials after processed by ball milling are then added into a carbohydrate solution and dispersed uniformly, and further, the materials are baked so as to make a solvent to volatilize perfectly until a slurry-shaped substance is formed; moreover, a concentrated sulfuric acid is added into the prepared slurry-shaped substance to stir uniformly, and the prepared slurry-shaped substance is then laid aside for dehydration and carbonization for 1 to 5 hours; finally, water is added into the obtained slurry-shaped substance for suction, filtration, washing, drying, crush and sieving so as to obtain the composite negative electrode material; in addition, the composite negative electrode material comprises the silicon with the content of 10% to 80% by wt. and the graphite with the content of 10% to 60% by wt., and the rest is carbon. The method has the advantages of simple operating procedure and low cost, and the prepared silicon /carbon /graphite composite materiel has the advantages of excellent charge and discharge performances.
Description
Technical field
The present invention relates to a kind of lithium ion battery silicon/carbon/composite cathode material of silicon/carbon/graphite and preparation method thereof, belong to field of electrochemical power source.
Background technology
Through numerous researchers' effort, the carbon class negative material of practical application is at present almost near its theoretical capacity 376mAh/g, and therefore, the just necessary employing of performance that further improve lithium ion battery is new, has the more negative material of height ratio capacity.Have the bianry alloy or the intermetallic compound of many high power capacity to use as negative material, wherein silicon is the most attractive a kind of, and to have an atomic weight little because of it, and lithium-inserting amount (forms Li greatly in theory
22Si
5Specific capacity can reach 4200mAh/g) and low characteristics such as (less than 0.5V) of embedding lithium current potential.Although silicon possesses these advantages, but realize having run in the commercial process many problems at it, to the destruction of the crystal structure of silicon, will produce very big volumetric expansion subsequently when these problems all come from alloying basically, the silicon grain efflorescence was lost efficacy, and cycle performance worsens.Address this problem two kinds of methods are arranged usually: the one, deposition on collector (radio frequency deposition or vacuum moulding machine) obtains silicon thin film, the advantage of this method is not need to add other component in the electrode, shortcoming is that this preparation process is not suitable for large-scale production, and after the thickness of silicon fiml surpasses 1 micron, the diffusion length of lithium ion increases, the corresponding increase of resistance and stress.The 2nd, prepare siliceous composite material, modal is silicon/carbon composite.Silicon/carbon composite has two kinds of models, and a kind of is " hud typed " structure, promptly on silicon grain by chemical vapour deposition (CVD) one deck carbon simple substance, can suppress the efflorescence of silicon grain and can avoid contingent silicon grain agglomeration in the charge and discharge process again.Another kind is " cake type " structure, is about to silicon grain and at first is dispersed in a kind of organic substance presoma, organic substance is carried out high temperature carbonization again and handles, and obtains silicon grain and is dispersed in silicon/carbon composite in the carbon base body.Though the affiliation that adds of carbon causes the specific capacity of composite material to descend to some extent, it still can be used as the desirable substitute of carbon class negative material.The problem that exists is exactly that organic substance carries out the temperature very high (generally at 900～1000 ℃) that charing is handled, and carbonization process also needs inert atmosphere protection, and airtight relatively operating system makes that the dispersion effect of silicon grain is often also bad.
Goal of the invention
Purpose of the present invention is exactly to explore a kind of silicon/carbon that at room temperature carries out/graphite composite material novel preparation method, simplifies the operation, and reduces cost.Its basic principle is exactly to utilize the dehydration characteristic of the concentrated sulfuric acid, and hydrogen during scattered in advance silicon (graphite)/carbohydrate forerunner is expected and oxygen carry out original position with the form of water and removes, and directly obtain silicon/carbon/graphite composite material.Prepared silicon/carbon/graphite composite material has the excellent charging and discharging performance.
Composite material involved in the present invention is made of jointly elemental silicon, graphite granule and amorphous carbon.Wherein elemental silicon and graphite are to obtain by silica flour and graphite are carried out mixing and ball milling, and amorphous carbon then is to obtain by carbohydrate is carried out dehydration carbonization.Requirement for carbohydrate is: 1. composition can be expressed as C
mH
2m-2O
n, (m and n are respectively carbon atom and the oxygen atomicity that contains in the organic molecule, m 〉=6, n 〉=5); 2. can in suitable, volatile solvent, dissolve; 3. with the concentrated sulfuric acid other redox reaction does not take place.The calculating of silicone content is based on the basis that the complete dehydration carbonization productive rate of carbohydrate is 1200m/ (14m+16n-2) wt% and carries out in the composite material.The content range of silicon is 10-80wt% in the composite material involved in the present invention, and the addition of graphite is about 10-60wt%.When silicone content was lower than 5wt%, the specific capacity of composite material did not significantly improve; When silicone content surpassed 80wt%, the cycle performance of composite material did not significantly improve.In the Composite Preparation process, silica flour does not need to grind again and sieves behind the ball milling, and also without any need for inertia or reducibility gas protection, whole process of preparation is carried out in the system of opening wide during charing.In the material preparation process, silica flour and graphite mixing back are carried out high-energy ball milling under argon gas atmosphere.The high-energy ball milling time can adopt more than 10 hours, and powder is a nanoscale behind the ball milling like this, better effects if.Material behind the ball milling is joined in the carbohydrate saturated solution, treat that the ultrasonic back that is uniformly dispersed makes solvent evaporates complete with the infrared lamp baking, until forming the syrupy shape material.In the slurry that forms, add the concentrated sulfuric acid again, stir, left standstill dehydration carbonization 2 hours.Suction filtration behind the thin up filters the back and is washed till neutrality with deionized water, and is dry, pulverize, cross 200 mesh sieves and get final product.
Compare with the existing various preparation methods that contain silicon composite cathode material, the present invention has following characteristics:
(1) granularity requirements to silicon powder particle is low, can be directly with 300 purpose silica flours as raw material;
(2) graphite of Jia Ruing not only can improve the cycle performance of material, and the silica flour particle diameter reduces when also being beneficial to ball milling simultaneously;
(3) carbonization process carries out at normal temperatures, does not need heating, has reduced energy consumption;
(4) elemental silicon can be not oxidized in the carbonization process, therefore without any need for protective gas;
(5) silicon does not have other chemical reaction to take place in the carbonization process, and not seeing has SiC and SiO
2Generate mutually Deng impurity;
(6) in the carbonization process not with an organic solvent, environmentally friendly;
(7) sulfuric acid after the charing can be realized recycling after concentrating;
(8) operating procedure is simple, and running cost is low.
Description of drawings
Fig. 1 is the X-ray diffraction collection of illustrative plates of silicon/carbon/graphite composite material of obtaining, the diffraction maximum of elemental silicon as can be seen only therefrom, and do not have the diffraction maximum of other siliceous impurity to occur, illustrate in the preparation process silicon less than and the concentrated sulfuric acid tangible side reaction takes place.
Fig. 2 is the transmission electron microscope photo of silicon/carbon/graphite composite material, and silicon nanoparticle is dispersed in the carbon base body as can be seen, and carbon base body can stop silicon grain to be reunited again together when discharging and recharging, and produces new bulk effect.
Fig. 3 is for being that active material prepares electrode with silicon/carbon/graphite composite material, is cyclic voltammetry curve to electrode assembled battery with lithium metal.0.2V and 0V near reduction peak and the oxidation peak at 0.3V and 0.5V place illustrate that all silicon has participated in the embedding/dealkylation reaction of lithium ion.
Fig. 4 is for being that active material prepares electrode with pure silicon and silicon/carbon/graphite composite material, with lithium metal is cycle performance curve to electrode assembled battery, therefrom as can be seen through 5 circulation back pure silicon electrode capacities total losses almost, and silicon/carbon/graphite composite material electrode can discharge metastable capacity.
Embodiment
Below by the description of example and comparative example, further set forth substantive distinguishing features of the present invention and advantage.For convenience of description, at first earlier comparative example is narrated, and then described embodiment 1～4,, demonstrated effect of the present invention to compare with it.
Comparative example 1.
Silica flour (average grain diameter 0.2 μ m) and acetylene black and Kynoar (PVDF) are made slurry by 60: 20: 20 mass ratio in N-methyl pyrrolidone (NMP) medium, coat on the Copper Foil and carry out drying, make electrode film thus.With metallic lithium foil is to electrode, and polypropylene screen is a barrier film, 1MLiPF
6/ (PC+DMC) (1: 1) be electrolyte, at 0.1mA/cm
2Current density under, discharge and recharge experiment in the voltage range of 0.02-1.5V.Embedding lithium capacity is 3042mAh/g first, and taking off the lithium capacity is 2108mAh/g, and coulombic efficiency is 69%.The 10th time embedding lithium capacity is 13.7mAh/g, and taking off the lithium capacity is 12.1mAh/g, through 10 circulation volumes, 99% (with respect to taking off the lithium capacity first) of having decayed.Explanation is that the electrode capacity decay of active material is very fast with the pure silicon powder.
Embodiment 1.
5 gram silica flours (average grain diameter 0.2 μ m) are joined in the aqueous solution that is dissolved with 47.5 gram sucrose, the mixing drying, to add concentrated sulfuric acid dehydration carbonization 2 hours in the slurry that obtain again, dilution, filtration, washing to neutral final vacuum drying obtain silicon/carbon composite of siliceous 20wt%.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Embedding lithium capacity is 1365mAh/g first, and taking off the lithium capacity is 1115mAh/g, and coulombic efficiency is 82%.The 10th time embedding lithium capacity is 838mAh/g, and taking off the lithium capacity is 784mAh/g, has decayed 30% through 10 circulation volumes, than the pure silicon electrode significant improvement has been arranged.
Embodiment 2.
With 300 order silica flours and graphite powder according to 2: 1 quality than mixing and ball milling (ratio of grinding media to material 10: 1) 5 hours.Join behind the ball milling in the aqueous solution that is dissolved with sucrose, dry behind the ultrasonic dispersion mixing, in the slurry that obtains, added concentrated sulfuric acid dehydration carbonization 2 hours again, dilution, filter, washing to neutral final vacuum drying obtains siliceous, amorphous carbon and graphite is 20%, 10% and 70% composite material.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Embedding lithium capacity is 1435mAh/g first, and taking off the lithium capacity is 1084mAh/g.The 10th time embedding lithium capacity is 989mAh/g, and taking off the lithium capacity is 935mAh/g, has decayed 19% through 10 circulation volumes, and the cyclical stability of composite material has had further improvement.
Embodiment 3.
It is 20%, 20% and 60% composite material that 300 purpose silica flours and graphite powder are prepared siliceous, amorphous carbon and graphite with 1: 1 mass ratio according to the method for embodiment 2.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Embedding lithium capacity is 1465mAh/g first, and taking off the lithium capacity is 953mAh/g.The 10th time embedding lithium capacity is 905mAh/g, and taking off the lithium capacity is 850mAh/g, has decayed 9% through 10 circulation volumes, and the addition that increases graphite can further improve the cycle performance of material.
Embodiment 4.
It is 20%, 30% and 50% composite material that 300 purpose silica flours and graphite powder are prepared siliceous, amorphous carbon and graphite with 2: 3 mass ratio according to the method for embodiment 2.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Embedding lithium capacity is 1507.9mAh/g first, and taking off the lithium capacity is 847.1mAh/g.The 30th time embedding lithium capacity is 800.2mAh/g, and taking off the lithium capacity is 767.2mAh/g, has only decayed 9.4% through 30 circulation volumes.As seen, the cyclical stability of composite material has had remarkable improvement.
It is 20%, 40% and 40% composite material that 300 purpose silica flours and graphite powder are prepared siliceous, amorphous carbon and graphite with 1: 2 mass ratio according to the method for embodiment 2.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Embedding lithium capacity is 1543mAh/g first, and taking off the lithium capacity is 802mAh/g.The 30th time embedding lithium capacity is 766mAh/g, and taking off the lithium capacity is 682mAh/g, has decayed 15% through 30 circulation volumes.As seen the addition that continues increase graphite is unfavorable to the material cycle performance.
Composite electrode among the embodiment 4 is discharged and recharged under 0.2C, and embedding lithium capacity is 1726mAh/g first, and taking off the lithium capacity is 1005.2mAh/g, and the 30th time embedding lithium capacity is 657.9mAh/g, and taking off the lithium capacity is 637.3mAh/g; 0.5C under discharge and recharge, embedding lithium capacity is 1309.1mAh/g first, taking off the lithium capacity is 761.4mAh/g, the 30th time embedding lithium capacity is 633.4mAh/g, taking off the lithium capacity is 616.6mAh/g; Discharge and recharge under the 1C, embedding lithium capacity is 922.5mAh/g first, and taking off the lithium capacity is 460.4mAh/g, and the 30th time embedding lithium capacity is 595.4mAh/g, and taking off the lithium capacity is 582.6mAh/g.Even as seen discharging and recharging than under the high magnification, this electrode capacity still can better keep.
Claims (7)
1. lithium ion battery silicon/carbon/composite cathode material of silicon/carbon/graphite is characterized in that this composite negative pole material is made up of elemental silicon, graphite granule and amorphous carbon.
2. by the described a kind of lithium ion battery silicon/carbon of claim 1/composite cathode material of silicon/carbon/graphite, the content range that it is characterized in that elemental silicon in this composite negative pole material is 10-80wt%, and the content range of graphite granule is 10-60wt%, the amorphous carbon surplus.
3. the preparation method of lithium ion battery silicon/carbon/composite cathode material of silicon/carbon/graphite, it is characterized in that and to carry out high-energy ball milling after silica flour and the graphite mixing, then the material behind the ball milling is joined in the carbohydrate saturated solution, the back baking of being uniformly dispersed makes in the saturated solution solvent evaporates complete, until forming slurry like material, in the slurry that forms, add the concentrated sulfuric acid again, stir, left standstill dehydration carbonization 1-5 hour, add the water suction filtration, washing, dry, pulverize, sieving gets final product.
4. by the preparation method of the described a kind of lithium ion battery silicon/carbon of claim 3/composite cathode material of silicon/carbon/graphite, it is characterized in that silica flour and graphite mixed that to carry out high-energy ball milling be to carry out under argon gas atmosphere.
5. by the preparation method of claim 3 or 4 described a kind of lithium ion battery silicon/carbon/composite cathode material of silicon/carbon/graphite, it is characterized in that the requirement of described carbohydrate is:
(1) composition is expressed as C
mH
2m-2O
n, m and n are respectively carbon atom and the oxygen atomicity that contains in the organic molecule, m 〉=6, n 〉=5;
(2) can in volatile solvent, dissolve;
(3) with the concentrated sulfuric acid other redox reaction does not take place.
6. by the preparation method of claim 3 or 4 described a kind of lithium ion battery silicon/carbon/composite cathode material of silicon/carbon/graphite, it is characterized in that described carbohydrate is a sucrose.
7. by the preparation method of claim 3 or 4 described a kind of lithium ion battery silicon/carbon/composite cathode material of silicon/carbon/graphite, it is characterized in that the preferred time of described ball milling is more than 10 hours.
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Families Citing this family (15)
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|---|---|---|---|---|
| CN101442124B (en) * | 2007-11-19 | 2011-09-07 | 比亚迪股份有限公司 | Method for preparing composite material of lithium ion battery cathode, and cathode and battery |
| JP5357565B2 (en) * | 2008-05-27 | 2013-12-04 | 株式会社神戸製鋼所 | Negative electrode material for lithium ion secondary battery, manufacturing method thereof, and lithium ion secondary battery |
| CN101304088B (en) * | 2008-06-27 | 2013-06-26 | 三峡大学 | Method for preparing sphericity lithium ion battery silicon/stannum binary lithium-storing precursor composite cathode material |
| CN102157731B (en) | 2011-03-18 | 2015-03-04 | 上海交通大学 | Silicon and carbon compound anode material of lithium ion battery and preparation method of silicon and carbon compound anode material |
| CN102916167B (en) * | 2011-08-04 | 2016-08-03 | 上海交通大学 | Mesoporous silicon compound as lithium ion battery negative material and preparation method thereof |
| CN103022435B (en) * | 2011-09-20 | 2016-05-04 | 宁波杉杉新材料科技有限公司 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
| CN103378368B (en) * | 2012-04-17 | 2016-06-15 | 万向电动汽车有限公司 | A kind of silicon cathode lithium ion battery and manufacture method |
| KR102069120B1 (en) | 2012-05-21 | 2020-01-22 | 이머리스 그래파이트 앤드 카본 스위춰랜드 리미티드 | Surface-modified carbon hybrid particles, methods of making, and applications of the same |
| CN102891297B (en) * | 2012-11-10 | 2015-05-13 | 江西正拓新能源科技股份有限公司 | Silicon-carbon composite material for lithium ion battery and preparation method thereof |
| CN103367732A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Carbon-coating method of negative electrode material of lithium ion secondary battery |
| CN105084366A (en) * | 2014-05-15 | 2015-11-25 | 国家纳米科学中心 | Method for preparing nano-sized silicon and silicon/carbon composite material by using silica fume as raw material and application thereof |
| CN105680013A (en) * | 2016-01-26 | 2016-06-15 | 湖南有色金属研究院 | Preparation method for silicon/graphite/carbon composite negative electrode material of lithium ion battery |
| EP3535794B1 (en) * | 2016-11-07 | 2022-03-02 | GRST International Limited | Method of preparing battery anode slurries |
| CN109686975A (en) * | 2018-12-05 | 2019-04-26 | 桑德集团有限公司 | A kind of hard charcoal negative electrode material and preparation method thereof |
| CN114229870B (en) * | 2021-12-08 | 2022-09-23 | 宜宾锂宝新材料有限公司 | In-situ carbon-coated Prussian blue positive electrode material and preparation method and application thereof |
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| JP2000203818A (en) * | 1999-01-13 | 2000-07-25 | Hitachi Chem Co Ltd | Composite carbon particle, its production, negative pole material, negative pole for lithium secondary battery or cell and lithium secondary battery or cell |
| JP2004349164A (en) * | 2003-05-23 | 2004-12-09 | Nec Corp | Negative electrode active material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000203818A (en) * | 1999-01-13 | 2000-07-25 | Hitachi Chem Co Ltd | Composite carbon particle, its production, negative pole material, negative pole for lithium secondary battery or cell and lithium secondary battery or cell |
| JP2004349164A (en) * | 2003-05-23 | 2004-12-09 | Nec Corp | Negative electrode active material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
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