CN100426563C - Production of negative material of high-capacity lithium-ion battery with tin-antimony-silicon alloy - Google Patents

Production of negative material of high-capacity lithium-ion battery with tin-antimony-silicon alloy Download PDF

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CN100426563C
CN100426563C CNB200510012296XA CN200510012296A CN100426563C CN 100426563 C CN100426563 C CN 100426563C CN B200510012296X A CNB200510012296X A CN B200510012296XA CN 200510012296 A CN200510012296 A CN 200510012296A CN 100426563 C CN100426563 C CN 100426563C
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ion battery
alloy
lithium ion
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snsbsi
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CN1747201A (en
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赵海雷
郭洪
仇卫华
尹朝丽
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides a preparation method for a SnSbSi negative electrode material of an alloy lithium ion battery with high capacity, which belongs to the field of a lithium ion battery. The present invention is characterized in that tin and antimony oxides and silicon powder are prepared according to the proportion of Sn, Sb and Si in the generated alloy composite, and then, carbon powders in appropriate proportion are introduced as reducing agents; after being mixed and ground uniformly, the obtained mixture is in the atmosphere of flowing inert argon gas while the temperature is raised to 800 DEG C to 1100 DEG C at a temperature raising rate of 5 to 30 DEG C/minute, and moreover, the temperature keeps constant for 1 to 3 hours; then, a power supply is switched off, and the mixture is cooled by means of a furnace to room temperature. The present invention has the advantages that the cost is low, the preparation technology and process is simple, the synthetic SnSbSi alloy powder has uniform and small particle size and favorable degree of crystallization, and the prepared SnSbSi negative electrode material of the lithium ion battery has high specific capacity and stable cycle performance; in addition, the highest reversible capacity can reach up to 1017 mAh/g, and the specific capacity can still remain about 90% after 10 cycles.

Description

A kind of preparation method of negative material of high-capacity lithium-ion battery with tin-antimony-silicon alloy
Technical field
The invention belongs to the lithium ion battery field, a kind of preparation method of high power capacity SnSbSi alloy lithium ion battery negative material is provided especially.
Background technology
Information industry, especially 3C articles for use (Cellular phone, Camocorder Computer), the development of EV (electric automobile), HEV (hybrid-electric car) and military extraordinary electronic equipment, has proposed more and more higher requirement to the energy density and the cycle performance of battery.Lithium ion battery is exactly the latest generation rechargeable battery that has grown up behind the MH-Ni battery since the nineties, it has the operating voltage height, energy density is big, fail safe good, light weight, self discharge are little, have extended cycle life, memory-less effect, advantage such as pollution-free, becomes an emphasis of modern new energy development.
Present business-like lithium ion battery negative material adopts carbon class material mostly, but the lithium storage content that studies show that it is lower, very near its theoretical specific capacity (the theory storage lithium amount as graphite is 372mAh/g), the space of further improving its specific capacity is very limited at present for its actual specific capacity.In addition, material with carbon element is when the embedding lithium, and its electrode potential and lithium metal are close, and when battery overcharge, the easy precipitating metal lithium of carbon electrodes forms dendrite and causes short circuit, has a strong impact on the fail safe of battery.Therefore, exploitation specific capacity height, fail safe lithium ion battery negative material good, that cycle performance is good become present material worker and electrochemist's research focus.
Many metals and semimetal (as: Al, Mg, Ga, In, Sn, Zn, Cd, Si, Ge, Pb, Sb, Bi, Au, Ag, Pt etc.) can form alloy with lithium, and their storage lithium amount is considerable, wherein the theoretical specific capacity of metallic tin is 990mAh/g, and silicon is 4200mAh/g, far above the graphite-like negative material.But Li and single metal formation alloy Li xDuring M, can be attended by very big volumetric expansion (2-3 doubly), this will cause electrode cycle performance variation, thereby hinder the practical application of alloy anode.Be the change in volume that suppresses or mitigation is followed in the removal lithium embedded process, usually take off the electrode matrix of embedding as Li with binary or multicomponent alloy, the research of activity/inactive metal alloy nano-material becomes the focus of lithium ion battery negative material research in recent years, as Sn/SnSbx, Sn/SnAgx, Sn/SnFe, nanometer-Si/C and nanometer-SnSb.Wherein one of metal mostly be that quality is softer, ductility inert matter preferably, variation to volume has stronger adaptability, when Li takes off embedding, can cushion the mechanical stress of bringing owing to the active material change in volume, thereby make alloy material have good cyclical stability, promptly prepare alloy or intermetallic compound base negative material.In the alloy anode of being studied, the most noticeable is Sn and Si base alloy.At present, many researchers are devoted to the modification and the optimal design of the high lithium storage materials of this two class.In order to cushion the bigger change in volume that the Sn sill is produced in the removal lithium embedded process, Besenhard group is compound with Sn and Sb, because Sb also can and have higher capacity (Li with Li chemical combination 3Sb, 660mAh/g), thereby the SnSb composite material demonstrates higher electrochemistry capacitance.Simultaneously, Sn is different with the removal lithium embedded current potential of Sb, thereby thereby the change in volume that mutually can the buffering reaction phase be produced of unreacted guaranteed that the SbSb composite material has good cyclical stability (M.Winter and J.O.Besenhard, Electrochimica Acta, 1999,45:31-50).(CN1317841A) the tin class organic compound that proposes with many carbon-chain structures in is a presoma, method by solid phase heating is decomposed it and is evenly disperseed and be embedded in the carrier carbon material surface, form the Sn-C composite negative pole material, this material list reveals higher electrochemical lithium storage content.These materials adopt the chemical liquid phase reduction more, and the method that electro-deposition or chemical heat are decomposed is prepared, thereby complicated process of preparation, the cost height, and productive rate is low.
Adopt ductility such as Ni, Fe good metal material and Si compound, formation is the activated centre with Si, with the inert metal material is the activity/inertia compound system of dispersible carrier, can improve cycle performance (the X.Q.Cheng and P.F.Shi of material, Journal of Alloys and Compounds, 2005,391:241-244).European patent (disclosing communique No. 0883199) proposes the solid solution that formed by silicon and tin or intermetallic compound as lithium ion battery negative material.Such material uses simple metal more, finishes the alloying process of material by high energy ball mill method, this method length consuming time (generally more than 200h), and use simple metal to increase the production cost of negative material, and its process conditions harshness, the cost height, productive rate is low.
Thereby it is low to research and develop a kind of cost, is convenient to large-scale production, and the multicomponent alloy negative material of while electrochemical specific capacity height, good cycling stability is for promoting the practical application of alloy material in lithium ion battery to have great importance.
Summary of the invention
The objective of the invention is to: the preparation method that a kind of lithium ion battery SnSb/Si ternary alloy anode material is provided, adopt carbothermic method, utilize the oxide of carbon dust as reducing agent reduction tin and antimony, the silica flour that directly mixes in raw material prepares the alloy material of cathode of different SnSb/Si ratios.Not only cost is low for this method, preparation process is simple, and the uniform particles of synthetic SnSb/Si alloy powder is tiny, and degree of crystallinity is good, SnSbSi lithium ion battery negative material specific capacity height, the good cycling stability prepared.
The present invention adopts the concrete technology of the synthetic SnSb/Si alloy material of cathode of high temeperature chemistry reduction technique to be:
With micron order, submicron order or nanoscale SnO 2, Sb 2O 3, Si powder and activated carbon or carbon black powder carry out weighing proportioning: SnO 2And Sb 2O 3Addition press Sn and Sb atomic ratio and calculated in 3: 1～1: 3, the addition of Si accounts for 20～80% (atomic percents of total alloy amount, with respect to Sn+Sb+Si), the addition of activated carbon or carbon black is calculated by chemical formula (1), x:2y=3 wherein: 1～1: 3, z:(x+2y+z)=0.2～0.8.Oxidized for preventing Si, the consumption of C can excessive 5～50 atom %.
xSnO 2+ySb 2O 3+(2x+3y)C+zSi＝Sn xSb 2ySi z+(2x+3y)CO (1)
Adopt mechanical dry method mixed or wet mixing that it is mixed; Mixture places the heating furnace that is connected with flowing nitrogen or argon gas atmosphere, reaches temperature required 800～1100 ℃ with 5～30 ℃/minute heating rates, is incubated 1～3 hour; Outage cools to room temperature naturally with the furnace then.SnO in the control initiation material 2, Sb 2O 3With the ratio of Si, can effectively control the ratio of three kinds of elements in the gained SnSbSi product.
According to calculation of thermodynamics, the oxide of tin and antimony (450～650 ℃) under relatively low temperature can be reduced to metal by C, again because the fusing point of Sn, Sb is lower: be respectively 232 ℃ and 631 ℃, the metal Sn that restores, Sb have higher activity, and the easy and mutual alloying of Si generates SnSbSi alloy or intermetallic compound.Simultaneously, Sn, Sb, Si three all can close with lithiumation, and show higher lithium storage content, and three's removal lithium embedded current potential is close, but different.Volumetric expansion and the mechanical stress that unreacted mutually can the buffering reaction phase be produced in the process of Sn, Sb, Si and lithium reaction like this, thereby can improve the structural stability of composite material.The present invention adopts the high temeperature chemistry reduction technique; utilize carbon dust as reducing agent; tin oxide, antimony oxide, silicon and carbon dust are evenly mixed, place the sintering furnace that is connected with under the protective atmosphere to carry out sintering, be incubated after 1-3 hour and can obtain end product SnSb/Si alloy composite materials with the stove cooling.
The invention has the advantages that technical process is simple, consuming time less, the productive rate height.Synthesize SnSb/Si alloy degree of crystallinity height, be 5～500 microns polycrystalline particle, thereby specific area is lower, serious reunion and surface oxidation be difficult for to take place, thereby have reduced the irreversible capacity of negative material.Simultaneously, the tactic pattern of ternary alloy three-partalloy has cushioned the change in volume of material in the removal lithium embedded process, and it is taken place step by step, thereby has improved the cyclical stability of material.And the uniform particles of synthetic SnSbSi alloy powder is tiny, degree of crystallinity is good, SnSbSi lithium ion battery negative material specific capacity height, the stable cycle performance prepared, reversible capacity is up to 1017mAh/g, and specific capacity remains on about 90% after 10 circulations.
Description of drawings
Fig. 1 is the XRD figure of the synthetic SnSb/Si of carbon thermal reduction of the present invention, and the ratio of Sn, Sb, Si is 2: 2: 3.5, and firing temperature is 900 ℃.
Fig. 2 is specific capacity-cycle-index curve of the synthetic SnSb/Si of carbon thermal reduction of the present invention, SnO 2, Sb 2O 3With the ratio of Si be 2: 2: 3.5, firing temperature is 900 ℃.
Embodiment
Embodiment 1:
With SnO 2(purity 99.9%), Sb 2O 3(purity 99.9%), Si powder (purity＞98%) and activated carbon (purity＞99%) are initial feed, 2: 1: 3.5 in molar ratio: 10.5 prepare burden (be equivalent to Sn: Sb: the Si atomic ratio is 2: 2: 3.5), after grinding mixture evenly, place that the heating rate with 5 ℃/min is elevated to 900 ℃ under the mobile argon gas atmosphere, be incubated 2 hours, outage naturally cools to room temperature then.The XRD material phase analysis result of gained sample shows that synthetic product is SnSb and Si, does not have the existence of any oxide impurity phase.
The conductive agent acetylene black that synthetic material is added 13wt%, the binding agent PVDF of 12wt% makes slurry, evenly be applied on the copper platinum, after the oven dry, block circular pole piece, form test cell, carry out the constant current charge-discharge experiment with lithium metal, charging and discharging currents is 100mA/g, and the charging/discharging voltage scope is controlled between the 0.01-1.2V.The initial reversible capacity of SnSb/Si negative material of preparation is 1017mAh/g, and the specific capacity that circulates after ten times is 905mAh/g, and capability retention is 89%.
Embodiment 2:
With SnO 2(purity 99.9%), Sb 2O 3(purity 99.9%), Si powder (purity＞98%) and activated carbon (purity＞99%) are initial feed, 4: 1: 2 in molar ratio: 9.5 prepare burden (atomic ratio that is equivalent to Sn: Sb: Si is 2: 1: 1), after grinding mixture evenly, place under the mobile argon gas atmosphere, heating rate with 10 ℃/min is elevated to 1000 ℃, be incubated 2 hours, outage naturally cools to room temperature then.The XRD material phase analysis of gained sample shows that synthetic product is Sn, and SnSb and Si do not have other oxide and exist mutually.
The conductive agent acetylene black that synthetic material is added 13wt%, the binding agent PVDF of 12wt% makes slurry, evenly be applied on the copper platinum, after the oven dry, block circular pole piece, form test cell, carry out the constant current charge-discharge experiment with lithium metal, charging and discharging currents is 100mA/g, and the charging/discharging voltage scope is controlled between the 0.01-1.2V.The initial reversible capacity of the SnSb/Si alloy material of cathode of preparation is 829mAh/g.The specific capacity that circulates after ten times is 750mAh/g, and capability retention is 90%.

Claims (1)

1, a kind of preparation method of SnSb/Si alloy lithium ion battery negative material adopts carbothermic method, utilizes the oxide of carbon dust as reducing agent reduction tin and antimony, and the silica flour that directly mixes in raw material prepares the alloy material of cathode of different SnSb/Si ratios; Concrete technology is:
A, with micron order, submicron order or nanoscale SnO 2, Sb 2O 3, Si powder and activated carbon or carbon black powder carry out weighing proportioning: SnO 2And Sb 2O 3Addition press Sn and Sb atomic ratio and calculated in 3: 1～1: 3, the atomic percent that the addition of Si accounts for total alloy amount Sn+Sb+Si is 20～80%, the addition of activated carbon or carbon black is pressed chemical formula: xSnO 2+ ySb 2O 3+ (2x+3y) C+zSi=Sn xSb 2ySi z+ (2x+3y) CO calculates, x: 2y=3 wherein: 1～1: 3, and z: (x+2y+z)=0.2～0.8; Oxidized for preventing Si, excessive 5～50 atom % of the consumption of C;
B, employing mechanical dry are mixed or the method for wet mixing mixes it; Mixture places the heating furnace that is connected with flowing nitrogen or argon gas atmosphere, reaches temperature required 800～1100 ℃ with 5～30 ℃/minute heating rates, is incubated 1～3 hour; Outage cools to room temperature naturally with the furnace then, obtains end product SnSb/Si alloy lithium ion battery negative material.
CNB200510012296XA 2005-08-03 2005-08-03 Production of negative material of high-capacity lithium-ion battery with tin-antimony-silicon alloy Expired - Fee Related CN100426563C (en)

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CN100373664C (en) * 2006-04-07 2008-03-05 北京科技大学 Preparation method for high-capacity Sn-Ni alloy compound as lithium ion battery negative electrode material
CN101662018B (en) * 2009-09-22 2012-07-04 西安交通大学 Method for preparing Sn-Sb-Ag alloy nano particles of anode materials of lithium ion batteries
CN102110806B (en) * 2009-12-23 2013-07-24 上海杉杉科技有限公司 Negative electrode material of lithium ion battery and preparation method thereof
US9373839B2 (en) 2011-12-13 2016-06-21 Samsung Sdi Co., Ltd. Negative electrode active material and secondary battery including the same
CN102544461A (en) * 2012-02-17 2012-07-04 电子科技大学 Anode material of lithium-ion battery and method for preparing anode material
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
CN104393268B (en) * 2014-11-06 2016-08-17 深圳职业技术学院 The preparation method of the SnSb/ CNT composite negative pole material that a kind of aeroge is modified
CN105742575B (en) * 2016-02-02 2018-02-06 北京理工大学 A kind of method that polyvinyl alcohol crosslinked carbonization of gelatin in situ prepares the porous silicium cathode of lithium ion battery

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EP1039568A1 (en) * 1998-09-18 2000-09-27 Canon Kabushiki Kaisha Electrode material for negative pole of lithium secondary cell, electrode structure using said electrode material, lithium secondary cell using said electrode structure, and method for manufacturing said electrode structure and said lithium secondary cell
CN1534812A (en) * 2003-03-28 2004-10-06 日立麦克赛尔株式会社 Negative for non-equeous secondary cell and non-aqueous secondary cell using the same
CN1595683A (en) * 2003-09-10 2005-03-16 中国科学院物理研究所 Nanometer metal or alloy composite material and preparation and usage thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1039568A1 (en) * 1998-09-18 2000-09-27 Canon Kabushiki Kaisha Electrode material for negative pole of lithium secondary cell, electrode structure using said electrode material, lithium secondary cell using said electrode structure, and method for manufacturing said electrode structure and said lithium secondary cell
CN1534812A (en) * 2003-03-28 2004-10-06 日立麦克赛尔株式会社 Negative for non-equeous secondary cell and non-aqueous secondary cell using the same
CN1595683A (en) * 2003-09-10 2005-03-16 中国科学院物理研究所 Nanometer metal or alloy composite material and preparation and usage thereof

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