CN100434362C - Method for preparig lithium secondary cell silicon/rich-lithium phase composite cathode material by high energy ball milling - Google Patents
Method for preparig lithium secondary cell silicon/rich-lithium phase composite cathode material by high energy ball milling Download PDFInfo
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Abstract
The present invention relates to a method for preparing a silicon/lithium-rich phase composite negative electrode material for a lithium secondary battery by means of high energy ball milling, which belongs to the field of electrochemical power source materials. The present invention comprises the following steps: firstly, a silicon monoxide and a metallic lithium are adopted as raw materials for synthesis, and the mixing mole ratio of the silicon monoxide to the metallic lithium is controlled to be 1: (1 to 2); then, the raw materials for synthesis are processed by ball milling after being mixed, and ball milling time is controlled to be 1 to 20 hours. Compared with other methods for preparing the composite negative electrode materials containing silicon, the method for preparing the composite negative electrode materials for the lithium secondary battery has the characteristics of few requirements for the raw materials, low synthesis temperature, low cost, high material specific capacity, good cycle performance, etc.
Description
Technical field
The present invention relates to the method that a kind of high-energy ball milling prepares lithium secondary battery silicon/rich lithium phase composite negative pole material, belong to electrochemical power source material field.
Background technology
Along with the gradually increase of people to portable electric appts degrees of dependence such as mobile phone, notebook computers, it is more and more important that battery seems.Compare with other battery system, lithium ion battery has more excellent chemical property, so up to now, it remains the optimal selection of secondary cell.In order to improve the capacity of lithium ion battery, a large amount of work concentrates in the negative material research of alternative graphite.Lithium can form alloy Li with these materials
xM (M is metals such as aluminium, tin, antimony, silicon), and can be reversible deviate from.Silicon is beyond doubt the most attractive in these materials, because its theoretical capacity is up to 4200mAh/g, and embedding lithium current potential low (less than 0.5V).But silicon electrode quick decay of capacity in working cycle has hindered its practicalization, and this decay is by embedding/take off volume change violent in the lithium process to cause.At this capacity attenuation problem, the domestic and international at present research to silicium cathode mainly concentrates on following five aspects: (1) obtains the thin film silicon electrode by chemical vapour deposition or thermal evaporation deposition, the cycle performance of electrode has obtained tangible improvement, but when the thickness of film surpassed 3 microns, cycle performance began again to worsen; (2) silica flour and a kind of material (graphite, amorphous carbon, silver, copper etc.) with good electrical electronic conductivity are carried out compound, the charge transfer resistance between the active material particle significantly reduces, and does not then improve significantly; (3) particle diameter of reduction silica flour, as adopting nano silica fume, specific storage can reach 1700mAh/g, but nano-silicon can be reunited again in circulation subsequently, produces new volume effect; (4) be that negative electrode active material reduces circulation time silicon first and changes the volume effect that produces by crystalline state to amorphous state with the amorphous silica powder, its cycle performance is better than common nano silica fume; (5) be negative electrode active material directly, earlier silicon cemented out when circulating the embedding lithium first, generate Li simultaneously with unbodied silicon monoxide
2O.Further during the embedding lithium and newly-generated silicon generation reversible alloying reaction, the volume change that produces in the working cycle can in time be absorbed by matrix, and the reunion again of nano-silicon can also be effectively avoided in the existence of matrix simultaneously.But this material is in that a large amount of lithium ion of circulation time can be because of irreversible generation Li first
2O and being consumed causes that current efficiency is very low first.Therefore, how to reduce round-robin irreversible capacity first, improving cycle efficiency is the research focus of oxide cathode.There has been the high-energy ball milling of utilization to promote reduction reaction at present, as metallic aluminium reduction silicon monoxide and the stannous report of elemental silicon reduction-oxidation, purpose is will obtain with the composite negative pole material of active material particle (silicon or tin) high dispersing in another kind buffering matrix, farthest to alleviate the volume effect that produces in the charge and discharge process.But also to introduce Li again after utilizing the metallic aluminium reduction
2O could obtain better cycle performance, and need carry out follow-up coating and handle, and operates more loaded down with trivial details; And can cause the specific storage of material sharply to descend owing to the existence of the bigger tin of nucleidic mass in the matrix material that obtains with the Si reduction tin protoxide.
Summary of the invention
Purpose of the present invention is exactly to promote a novel reduction reaction---the generation of " class disproportionation reaction " by high-energy ball milling, and preparation is used for the silicon/rich lithium phase composite negative pole material of lithium ion battery.Its ultimate principle is exactly to utilize the sharp impacts between the ball milling ball to provide activation energy for reaction, generates to contain silicon nanoparticle, and the matrix material of high dispersing in the rich lithium phase of another kind product.This material has advantages such as the big and good cycle of capacity, and operation such as does not also need to pulverize, sieve in the preparation process.
Matrix material involved in the present invention is made of mutually jointly rich lithiums such as nano level elemental silicon, positive lithium silicates.Synthesis material is oxide containing silicon (as silicon-dioxide, silicon monoxide) and metal (as basic metal, alkaline-earth metal etc.) with reductibility.Wherein the selection principle of oxide compound is: easily reduction, oxygen level is low, molecular weight is little; The choice criteria of metal is that reductibility is strong and nucleidic mass is little.According to above requirement, selecting silicon monoxide and metallic lithium respectively is synthesis material.The blending ratio of required silicon monoxide of matrix material involved in the present invention and metallic lithium is between 1: 1 (being mol ratio) was to 1: 2, and the oxide compound reduction not exclusively has a large amount of metallic lithium remnants when blending ratio is higher than 1: 2 when blending ratio is lower than 1: 1; The ball milling time, effect was best in 5～15 hours between 1～20 hour; In the material preparation process, silicon monoxide and metallic lithium are carried out high-energy ball milling after mixing under inert atmosphere or the vacuum, can continue under vacuum, to heat-treat (300～900 ℃) in case of necessity and promote reaction to carry out fully.The product that is obtained need not pulverized and sieve can be directly in order to the preparation electrode.
Compare with the existing various preparation methods that contain silicon composite cathode material, the present invention has following characteristics:
(1) ingredient requirement is not high, and cost is low;
(2) synthesis technique is simple, easily amplifies;
(3) material specific capacity height, good cycle;
(4) material has good structural stability under high magnification;
(5) synthesis temperature contains silicon composite (preparing as silicon/carbon composite) far below other about 900 ℃;
(6) particle diameter of elemental silicon little (about 10 nanometers) in the material, be evenly distributed;
(7) there is not other by product to generate in the building-up process, environmentally friendly.
Description of drawings
Fig. 1 is the X-ray diffraction collection of illustrative plates of material (b) after single silicon oxide (a) and the reactant mixing and ball milling, the diffraction peak that wherein has elemental silicon and positive lithium silicate, illustrate that metallic lithium restores elemental silicon, following reaction taken place in the existence explanation mechanical milling process of positive lithium silicate:
5SiO+6Li＝Li
2O+Li
4SiO
4+4Si
Fig. 2 is the high-resolution-ration transmission electric-lens photo of silicon/rich lithium phase composite materials, and silicon nanoparticle is dispersed in the matrix by positive lithium silicate and other rich lithium phase composite as can be seen.
Fig. 3 is the charging/discharging voltage curve of counter electrode assembled battery with the metallic lithium for being that active substance prepares electrode with single silicon oxide (a) and silicon/rich lithium phase composite materials (b) respectively.Compare with single silicon oxide electrode, the cycle performance of matrix material has obtained remarkable improvement.
Fig. 4 is the cycle performance curve under various charge-discharge magnifications of counter electrode assembled battery with the metallic lithium for being that active substance prepares electrode with silicon/rich lithium phase composite materials.Therefrom all discharge higher specific storage at various multiplying power lower electrodes as can be seen, and shown excellent cyclical stability.
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 comparative example is narrated, and then described embodiment 1～8,, demonstrated effect of the present invention to compare with it.
Comparative example 1
Silicon monoxide powder (300 order) and acetylene black and polyvinylidene difluoride (PVDF) (PVDF) are made slurry by 85: 10: 5 mass ratio in N-Methyl pyrrolidone (NMP) medium, coat on the Copper Foil and carry out drying, make electrode film thus.With the metallic lithium foil is counter electrode, and polypropylene screen is a barrier film, 1MLiPF
6/ (PC+DMC) (1: 1) be electrolytic solution, at 0.1mA/cm
2Current density under, discharge and recharge experiment in the voltage range of 0.02～1.5V.Embedding lithium capacity is 1816mAh/g first, and taking off the lithium capacity is 516mAh/g, and coulombic efficiency is 28.4%.The 10th time embedding lithium capacity is 317.9mAh/g, and taking off the lithium capacity is 302.8mAh/g, through 10 circulation volumes, 41.3% (with respect to taking off the lithium capacity first) of having decayed.Explanation is that the electrode capacity decay of active substance is very fast with the silicon monoxide powder.
Embodiment 1
In glove box 5 gram silicon monoxides (99.99%) and 0.78 gram metallic lithium (mol ratio 1: 1) mixing are placed in the stainless steel jar mill, add a certain amount of Stainless Steel Ball abrading-ball (ball material mass ratio is 16: 1) again, take out the sealing back.Ball milling is 10 hours under 475 rev/mins rotating speed, and the gained material is directly in order to the preparation electrode film.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Embedding lithium capacity is 1210.5mAh/g first, and taking off the lithium capacity is 470mAh/g, and coulombic efficiency is 38.82%.The 50th time embedding lithium capacity is 413mAh/g, and taking off the lithium capacity is 360mAh/g, has only decayed 9.1% through 50 circulation volumes, and more single silicon oxide electrode cycle performance has certain improvement.
Embodiment 2
In glove box 5 gram silicon monoxides (99.99%) and 0.78 gram metallic lithium (mol ratio 1: 1) mixing are placed in the stainless steel jar mill, add a certain amount of Stainless Steel Ball abrading-ball (ball material mass ratio is 16: 1) again, take out the sealing back.Carry out ball milling under 475 rev/mins rotating speed, gained material thermal treatment under vacuum (500 ℃) 5 hours can be directly in order to the preparation electrode film.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Embedding lithium capacity is 1100.5mAh/g first, and taking off the lithium capacity is 441mAh/g, and coulombic efficiency is 40%.The 50th time embedding lithium capacity is 389mAh/g, and taking off the lithium capacity is 378mAh/g, has only decayed 2.8% through 50 circulation volumes, and the more single silicon oxide electrode of cycle performance improves significantly.
Embodiment 3
5 gram silicon monoxides and 0.94 gram metallic lithium (mol ratio 5: 6) prepared according to the method for embodiment 1 contain nano-silicon/rich lithium matrix material mutually.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Embedding lithium capacity is 1341.7mAh/g first, and taking off the lithium capacity is 770.4mAh/g, and coulombic efficiency is 57.4%.The 50th time embedding lithium capacity is 767.7mAh/g, and taking off the lithium capacity is 762mAh/g, has only decayed 1.1% through 50 circulation volumes, and more single silicon oxide electrode has had significant improvement.
Embodiment 4. prepares 5 gram silicon monoxides and 1.1 gram metallic lithiums (mol ratio 5: 7) and contains nano-silicon/rich lithium matrix material mutually according to the method for embodiment 1.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Embedding lithium capacity is 1256.2mAh/g first, and taking off the lithium capacity is 625mAh/g.The 50th time embedding lithium capacity is 613.2mAh/g, and taking off the lithium capacity is 609.8mAh/g, has decayed 2.4% through 50 circulation volumes, and more single silicon oxide electrode has improvement, but cycle performance does not have the matrix material among the embodiment 2 good.
Embodiment 5
The composite electrode of preparation among the embodiment 3 is discharged and recharged under 0.2C, and embedding lithium capacity is 1157.3mAh/g first, and taking off the lithium capacity is 731.7mAh/g, and coulombic efficiency is 63.2%.The 50th time embedding lithium capacity is 700mAh/g, and taking off the lithium capacity is 684mAh/g, is 6.5% through 50 circulation volume rate of fall-off.
Embodiment 6
The composite electrode of preparation among the embodiment 3 is discharged and recharged under 0.4C, and embedding lithium capacity is 1327.4mAh/g first, and taking off the lithium capacity is 632.5mAh/g, and coulombic efficiency is 47.6%.The 50th time embedding lithium capacity is 610.2mAh/g, and taking off the lithium capacity is 581.9mAh/g, has decayed 8% through 50 circulation volumes.
Embodiment 7
The composite electrode of preparation among the embodiment 3 is discharged and recharged under 0.5C, and embedding lithium capacity is 1167.5mAh/g first, and taking off the lithium capacity is 616.2mAh/g, and coulombic efficiency is 52.8%.The 50th time embedding lithium capacity is 551.2mAh/g, and taking off the lithium capacity is 544mAh/g, has decayed 11.7% through 50 circulation volumes.
The composite electrode of preparation among the embodiment 3 is discharged and recharged under 1.0C, and embedding lithium capacity is 863.4mAh/g first, and taking off the lithium capacity is 356.7mAh/g, and coulombic efficiency is 41.3%.The 50th time embedding lithium capacity is 618.2mAh/g, and taking off the lithium capacity is 615.5mAh/g, has increased by 72% through 50 circulation volumes on the contrary than initial charge.As seen, experienced slowly at electrode when discharging and recharging under the high magnification that reactivation process discharges higher reversible capacity gradually, but can keep the integrity of electrode structure.
Claims (4)
1, a kind of high-energy ball milling prepares the method for lithium secondary battery silicon/rich lithium phase composite negative pole material, it is characterized in that comprising the steps:
(1) adopting silicon monoxide and metallic lithium is synthesis material;
(2) the mixing mol ratio of control silicon monoxide and metallic lithium is 1: 1～2;
(3) synthesis material being carried out high-energy ball milling after mixing under inert atmosphere or the vacuum handles.
2, the method for preparing lithium secondary battery silicon/rich lithium phase composite negative pole material by the described a kind of high-energy ball milling of claim 1 is characterized in that the high-energy ball milling time was at 1～20 hour.
3, the method for preparing lithium secondary battery silicon/rich lithium phase composite negative pole material by the described a kind of high-energy ball milling of claim 2 is characterized in that the high-energy ball milling time was at 5～15 hours.
4, the method for preparing lithium secondary battery silicon/rich lithium phase composite negative pole material by claim 1 or 2 or 3 described a kind of high-energy ball millings is characterized in that heat-treating under vacuum after high-energy ball milling is handled, and heat treated condition is 300～900 ℃.
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| 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 |
| CN101789506B (en) * | 2009-01-22 | 2015-11-25 | 中国科学院上海硅酸盐研究所 | Composite cathode material for lithium ion battery and preparation method |
| CN101814603B (en) * | 2009-02-23 | 2013-10-02 | 中国科学院上海硅酸盐研究所 | Glassy composite anode material and preparation method thereof |
| US8287772B2 (en) * | 2009-05-14 | 2012-10-16 | 3M Innovative Properties Company | Low energy milling method, low crystallinity alloy, and negative electrode composition |
| CN105655543A (en) * | 2014-11-13 | 2016-06-08 | 安泰科技股份有限公司 | Metal/oxide composite negative electrode material and preparation method thereof |
| CN106799497A (en) * | 2017-02-15 | 2017-06-06 | 中卫市创科知识产权投资有限公司 | A kind of nanometer Li-Si Alloy Powder production technology |
| CN108321368B (en) * | 2017-12-28 | 2020-07-17 | 合肥国轩高科动力能源有限公司 | Polymer-coated silicon/lithium metasilicate negative electrode material and preparation method thereof |
| CN109686930A (en) * | 2018-11-30 | 2019-04-26 | 天合光能股份有限公司 | A kind of richness lithium silicon substrate lithium ion battery negative material and preparation method thereof |
| CN111509213A (en) * | 2020-04-30 | 2020-08-07 | 广东工业大学 | Nano composite negative electrode material and preparation method thereof |
| CN113036108A (en) * | 2021-03-11 | 2021-06-25 | 昆山宝创新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN114835131A (en) * | 2022-03-21 | 2022-08-02 | 湖北钛时代新能源有限公司 | Preparation method of lithium silicate cathode material and lithium ion battery |
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| EP0582173A1 (en) * | 1992-07-29 | 1994-02-09 | Seiko Instruments Inc. | Non-aqueous electrolyte secondary battery and its production method |
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