CN101304088B - Method for preparing sphericity lithium ion battery silicon/stannum binary lithium-storing precursor composite cathode material - Google Patents
Method for preparing sphericity lithium ion battery silicon/stannum binary lithium-storing precursor composite cathode material Download PDFInfo
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Abstract
The invention relates to a preparation method of a silicon/tin binary lithium matrix composite cathode material of a spherical lithium ion battery, belonging to the field of electrochemical power sources. The invention is to mix the oxide containing silicon with metal lithium and graphite in inert atmosphere, to ball-grind mechanically and then to add oxide containing tin and go on ball-grinding to obtain the silicon/tin binary lithium matrix composite cathode material. Compared with other silicon composite cathode materials, the material provided by the invention has the advantages of high specific capacity, good circulation stability, simple synthesizing technique, easy operation and low material preparation cost without any heat processing procedures.
Description
Technical field
The invention belongs to field of electrochemical power source, be specifically related to a kind of preparation method's technology of lithium ion battery silicon/stannum binary lithium-storing precursor composite cathode material.
Background technology
Elemental silicon has the advantages such as theoretical capacity is high, embedding lithium current potential low (less than 0.5V) as lithium ion battery negative, but there is huge bulk effect in it when repeated charge, cause the active material particle efflorescence to be lost efficacy, capacity is decay fast therefore, makes the practical of silicium cathode be obstructed.Reducing the silicon grain size is an important directions of silicium cathode research to reduce that its absolute volume that produces changes in embedding/take off the lithium process.Existing studies show that, if with silicon grain be reduced to the micron or nanoscale just can improve significantly its cycle performance.At present in this respect research mainly with nanometer (＜100nm) silica flour is embedding/take off lithium main body, it is dispersed in the unconspicuous nonactive phase of another kind of change in volume, in amorphous carbon, to avoid silicon grain again to reunite, " electrochemistry sintering " occuring, and causes the new bulk effect of generation in the repeated charge process.Relevant research at first just relates to the preparation of nano silica fume.Common preparation method has Implantation, electrochemical etching, magnetron sputtering and induced with laser chemical vapour deposition (CVD) etc.In these methods, laser method is most possible and existing silicon process technology is compatible, has therefore obtained significant progress.Laser method prepares in the nano silica fume process, and the source of reaction power is mainly SiH
4Gas molecule is for CO
2The resonance absorption of laser, and be heated from separating generation supersaturation silicon steam, nucleation and growth is the nano-silicon particle in transport process.The preparation technology of laser method complexity and extremely low productive rate have determined that laser method prepares the sky high cost of nano silica fume, therefore are applied to the lithium battery industry unrealistic.When utilizing the chemical reaction original position to generate silicon nanoparticle, it being dispersed in other component will be a kind of convenient, technology of effectively preparing nanometer silicon composite material.Mechanochemical reaction is by means of grinding and crushing mechanism prepares a kind of common method of composite material.Ball-milling medium grinds to form particle tiny and that be evenly distributed by shear action and embrittlement mechanism repeatedly with material.Mechanochemical reaction is not only a kind of practical scale synthesizing new, the method for metasable state structural material, and it also can be used for causing some room temperature chemical reactions.Adopt the silicon composite cathode material that contains that the generation of mechanochemical reaction original position contains nano-silicon the absolute volume variation of particle can be reduced to greatest extent, the cyclical stability of material also can significantly improve.Desirable electrode material should be the electrons/ions mixed conductor, and silicon is low as a kind of semi-conducting material conductivity, unfavorable to the charge transfer between active material particle, therefore the simple reduction silicon grain size that relies on can not fundamentally solve the poor problem of its cycle performance.
Summary of the invention
The objective of the invention is to provide a kind of preparation method of sphericity lithium ion battery silicon/stannum binary lithium-storing precursor composite cathode material, by by means of mechanico-chemical reaction, nano-silicon, tin particles original position being synthesized, be dispersed in by the silicon/stannum binary lithium-storing precursor composite negative pole material in other product matrix, and by subsequent treatment, composite material be converted into particle diameter less than the spheric granules of 20 μ m.
The object of the present invention is achieved like this: a kind of preparation method of sphericity lithium ion battery silicon/stannum binary lithium-storing precursor composite cathode material, it is characterized in that: oxide containing silicon and lithium metal and graphite were mixed under inert atmosphere rear mechanical ball milling 5-10 hour, add to contain tin-oxide continuation ball milling 1-5 hour, the gained material obtained the silicon/stannum binary lithium-storing precursor composite negative pole material in 24 hours with the infrared lamp baking in air again.
Described oxide containing silicon is SiO
x, 0＜x≤1, the described tin-oxide that contains is SnO
x, 0＜x≤1.
Described oxide containing silicon is silicon monoxide, and the described tin-oxide that contains is stannous oxide.
The mixing ratio of oxide containing silicon and lithium metal is take molar ratio computing as 5: 7.
The mixing ratio that contains tin-oxide and oxide containing silicon with molar ratio computing between 1: 20 to 1: 1.
The preparation method of sphericity lithium ion battery silicon/stannum binary lithium-storing precursor composite cathode material provided by the invention, principle is exactly to utilize the difference of reactivity between silicon, tin-oxide and reducing agent, and a small amount of nanometer tin particle is incorporated in composite material containing silicon take silicon nanoparticle as single lithium-storing precursor.Tin particles can not only provide the part reversible capacity for composite material as another kind of lithium-storing precursor, also can improve electrically contacting between active material particle, keeps the integrality of electrodes conduct network, makes electrode can stably discharge reversible capacity.With comparing of other silicon composite cathode material, have following outstanding feature:
(1) high, the good cycling stability of material specific capacity;
(2) synthesis technique is simple, easy operating;
(3) without any need for heat treatment step;
(4) the material preparation cost is low.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples.
Fig. 1 is the X-ray diffraction collection of illustrative plates of prepared silicon/stannum binary lithium-storing precursor composite negative pole material, wherein can clearly find out the diffraction maximum of elemental silicon, metallic tin and lithium carbonate phase, this explanation lithium metal restores elemental silicon and metallic tin, and lithium metal residual in course of reaction transforms for the lithium carbonate phase.Calculate according to the Scherrer formula, the particle diameter of elemental silicon, metallic tin particle is respectively 10nm and 18nm, far below commercialization nano-silicon and nanometer tin.
Fig. 2 is the transmission electron microscope photo of silicon/stannum binary lithium-storing precursor composite negative pole material.Therefrom can find out, composite material is comprised of the spheric granules of particle diameter less than 20 microns.
Fig. 3 is the voltage curve that is respectively with the charge and discharge cycles of the composite material containing silicon (a) for preparing by mechanochemical reaction and silicon/stannum binary lithium-storing precursor composite negative pole material.Therefrom can find out, the silicon/stannum binary lithium-storing precursor composite negative pole material circulation time irreversible capacity that is used to form solid-electrolyte interphace (SEI) film first significantly reduces.
Fig. 4 is for take the silicon/stannum binary lithium-storing precursor composite negative pole material as active material preparation work electrode, take lithium metal as electrode and reference electrode being assembled into the cycle performance curve of button cell.After experiencing 30 circulations, material still can stably discharge the reversible capacity up to 551mAh/g, and capability retention is 88.4%.
Embodiment
Composite material involved in the present invention is comprised of phases such as nano-silicon, nanometer tin, lithium carbonates.Synthesis material is oxide containing silicon, SiO
x, 0＜x≤1, stanniferous oxide S nO
x, 0＜x≤1, metallic lithium foil and grinding aid graphite with strong reducing property.Lithium carbonate is the product that reaction obtains, and is mainly gradated in air by kish lithium after ball milling to form.The reaction that occurs in mechanical milling process is: SiO
x+ Li → Si+Li
4SiO
4+ Li
2O and SnO
x+ Li → Sn+Li
2O, the nano-silicon of generation, tin particles are dispersed in take lithium-containing compound in main buffering matrix.The present invention prepares the mixed proportion of the required silicon monoxide of composite material and lithium metal take mol ratio as 5: 7, the mixed proportion of required stannous oxide and silicon monoxide with molar ratio computing between 1: 20 and 1: 1.When the mixed proportion of stannous oxide and silicon monoxide is improved not obvious to the material cycle performance lower than mixed proportion during lower than 1: 20, generate the metallic tin particle during higher than 1: 1 when mixed proportion large, the change in volume that produces in the iterative cycles process causes the material cycle performance to worsen on the contrary.In the material preparation process, first with silicon monoxide, lithium metal and graphite, the graphite addition is 3～5% of silicon monoxide and lithium metal gross mass, after mixing under inert atmosphere, mechanical ball milling is 5～10 hours, add stannous oxide to continue ball milling 1～5 hour, the gained material toasts 24 hours for the preparation of electrode with infrared lamp in air again.
Below by the description of enforcement 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 1～4, to compare with it, demonstrated effect of the present invention.
Comparative example 1. is made slurry by the mass ratio of 85: 10: 5 with nano silica fume and acetylene black and Kynoar (PVDF) in 1-METHYLPYRROLIDONE (NMP) medium, coat on Copper Foil, through super-dry, rush film and press mold is made work electrode.Take metallic lithium foil as to electrode, the Celgard polypropylene screen is barrier film, 1MLiPF
6/ (PC+DMC) (1: 1) be electrolyte, at 0.15mA/cm
2Current density under, discharge and recharge experiment in the voltage range of 0.02-1.5V.Embedding lithium capacity is 3401mAh/g first, and taking off the lithium capacity is 2856mAh/g, and coulombic efficiency is 83.9%.The 30th time the circulation embedding lithium capacity be 1037mAh/g, taking off the lithium capacity is 854mAh/g, through 30 Capacity fadings 70%.Although explanation can partly suppress the change in volume of silicon grain take nano silica fume as active material, the reversible capacity decay is still very fast.
Embodiment 1. is placed on silicon monoxide and lithium metal in stainless steel jar mill according to mol ratio mixing in 5: 7 in glove box, add again the stainless steel ball abrading-ball after adding the graphite of silicon monoxide and lithium metal gross mass 3～5%, the ratio of grinding media to material that adopts is 16: 1, takes out after sealing.Carry out mechanochemical reaction synthetic on high energy ball mill, 475 rev/mins of rotating speeds, reaction time 5-10 hour, add again stannous oxide, with molar ratio computing SnO: SiO=1: 20, continue reaction and toasted 24 hours with infrared lamp in air after 1-5 hour, the gained material directly carries out electro-chemical test in order to prepare electrode.The assembling of electrode preparation method battery and test condition are all with Comparative Examples 1.Material embedding lithium capacity first is 975mAh/g, and taking off the lithium capacity is 771mAh/g, and coulombic efficiency is 79.1%.The circulation embedding lithium capacity of the 30th time is 621.5mAh/g, and taking off the lithium capacity is 609.1mAh/g, through 30 Capacity fadings 21%, purer nano-silicon electrode cycle performance has had certain improvement.
Embodiment 2. is placed on silicon monoxide and lithium metal in stainless steel jar mill according to mol ratio mixing in 5: 7 in glove box, add again the stainless steel ball abrading-ball after adding the graphite of silicon monoxide and lithium metal gross mass 3～5%, the ratio of grinding media to material that adopts is 16: 1, takes out after sealing.Carry out mechanochemical reaction synthetic on high energy ball mill, 475 rev/mins of rotating speeds, reaction time 5-10 hour, add again stannous oxide, with molar ratio computing SnO: SiO=1: 15, continue reaction and toasted 24 hours with infrared lamp in air after 1-5 hour, the gained material directly carries out electro-chemical test in order to prepare electrode.The assembling of electrode preparation method battery and test condition are all with Comparative Examples 1.Material embedding lithium capacity first is 892mAh/g, and taking off the lithium capacity is 704mAh/g, and coulombic efficiency is 78.9%.The circulation embedding lithium capacity of the 30th time is 603.5mAh/g, and taking off the lithium capacity is 591.4mAh/g, through 30 Capacity fadings 16%, the material in material cycle performance and embodiment 1 has further raising.
Embodiment 3. is placed on silicon monoxide and lithium metal in stainless steel jar mill according to mol ratio mixing in 5: 7 in glove box, add again the stainless steel ball abrading-ball after adding the graphite of silicon monoxide and lithium metal gross mass 3～5%, the ratio of grinding media to material that adopts is 16: 1, takes out after sealing.Carry out mechanochemical reaction synthetic on high energy ball mill, 475 rev/mins of rotating speeds, 10～15 hours reaction time, add again stannous oxide, SnO: SiO=1: 10, continue reaction and toasted 24 hours with infrared lamp in air after 1-5 hour, the gained material directly carries out electro-chemical test in order to prepare electrode.The assembling of electrode preparation method battery and test condition are all with Comparative Examples 1.Material embedding lithium capacity first is 831.6mAh/g, and taking off the lithium capacity is 623.1mAh/g, and coulombic efficiency is 74.9%.The circulation embedding lithium capacity of the 30th time is 559.2mAh/g, and taking off the lithium capacity is 551mAh/g, through 30 Capacity fadings 11.5%, the material cycle performance further improves.
Embodiment 4. is placed on silicon monoxide and lithium metal in stainless steel jar mill according to mol ratio mixing in 5: 7 in glove box, add again the stainless steel ball abrading-ball after adding the graphite of silicon monoxide and lithium metal gross mass 3～5%, the ratio of grinding media to material that adopts is 16: 1, takes out after sealing.Carry out mechanochemical reaction synthetic on high energy ball mill, 475 rev/mins of rotating speeds, 10～15 hours reaction time, add again stannous oxide, SnO: SiO=1: 5, continue reaction and toasted 24 hours with infrared lamp in air after 1-5 hour, the gained material directly carries out electro-chemical test in order to prepare electrode.The assembling of electrode preparation method battery and test condition are all with Comparative Examples 1.Material embedding lithium capacity first is 723mAh/g, and taking off the lithium capacity is 580.1mAh/g, and coulombic efficiency is 80.2%.The circulation embedding lithium capacity of the 30th time is 532.7mAh/g, and taking off the lithium capacity is 498mAh/g, through 30 Capacity fadings 14.3%.The material cycle performance is not as the material in embodiment 3, but reversible capacity also has reduction by a relatively large margin.
Claims (3)
1. the preparation method of a sphericity lithium ion battery silicon/stannum binary lithium-storing precursor composite cathode material, it is characterized in that: oxide containing silicon and lithium metal and graphite were mixed under inert atmosphere rear mechanical ball milling 5-10 hour, the mixing ratio of oxide containing silicon and lithium metal is take molar ratio computing as 5: 7, add again and contain tin-oxide continuation ball milling 1-5 hour, between 1: 20 to 1: 1, the gained material obtained the silicon/stannum binary lithium-storing precursor composite negative pole material in 24 hours with the infrared lamp baking to the mixing ratio that contains tin-oxide and oxide containing silicon in air with molar ratio computing.
2. the preparation method of sphericity lithium ion battery silicon/stannum binary lithium-storing precursor composite cathode material according to claim 1, it is characterized in that: described oxide containing silicon is SiO
x, 0＜x≤1, the described tin-oxide that contains is SnO
x, 0＜x≤1.
3. the preparation method of sphericity lithium ion battery silicon/stannum binary lithium-storing precursor composite cathode material according to claim 1 and 2, it is characterized in that: described oxide containing silicon is silicon monoxide, the described tin-oxide that contains is stannous oxide.
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| US8287772B2 (en) * | 2009-05-14 | 2012-10-16 | 3M Innovative Properties Company | Low energy milling method, low crystallinity alloy, and negative electrode composition |
| CN103545496B (en) * | 2013-10-18 | 2016-03-09 | 中国第一汽车股份有限公司 | A kind of preparation method of tin Si oxide composite negative pole material |
| 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 |
| CN109449416B (en) * | 2018-11-01 | 2022-03-08 | 中化国际(控股)股份有限公司 | Silica material and preparation method thereof |
| CN109686944B (en) * | 2018-12-21 | 2022-05-31 | 四川翔丰华新能源材料有限公司 | Carbon-coated lithium alloy composite electrode material and preparation method thereof |
| CN110707310B (en) * | 2019-10-29 | 2021-01-12 | 昆山宝创新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN111370693B (en) * | 2020-03-24 | 2022-12-27 | 洛阳联创锂能科技有限公司 | Preparation method of silica lithium anode material with high initial efficiency |
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| CN1761089A (en) * | 2005-10-27 | 2006-04-19 | 中国科学院上海硅酸盐研究所 | A kind of lithium ion battery silicon/carbon/composite cathode material of silicon/carbon/graphite and preparation method thereof |
| CN1850597A (en) * | 2006-04-28 | 2006-10-25 | 中国科学院上海硅酸盐研究所 | Method for preparig lithium secondary cell silicon/rich-lithium phase composite cathode material by high energy ball milling |
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| CN1761089A (en) * | 2005-10-27 | 2006-04-19 | 中国科学院上海硅酸盐研究所 | A kind of lithium ion battery silicon/carbon/composite cathode material of silicon/carbon/graphite and preparation method thereof |
| CN1850597A (en) * | 2006-04-28 | 2006-10-25 | 中国科学院上海硅酸盐研究所 | Method for preparig lithium secondary cell silicon/rich-lithium phase composite cathode material by high energy ball milling |
Non-Patent Citations (1)
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