CN105375012A - Si-Sn composite material used for Li-ion battery anode and preparation method thereof - Google Patents

Si-Sn composite material used for Li-ion battery anode and preparation method thereof Download PDF

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CN105375012A
CN105375012A CN201510850077.2A CN201510850077A CN105375012A CN 105375012 A CN105375012 A CN 105375012A CN 201510850077 A CN201510850077 A CN 201510850077A CN 105375012 A CN105375012 A CN 105375012A
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composite material
tin
silicon
preparation
ball milling
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CN105375012B (en
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朱正旺
吴金波
张海峰
王爱民
付华萌
***
李宏
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Institute of Metal Research of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 invention discloses a Si-Sn composite material used for a Li-ion battery anode and a preparation method thereof. The composite anode material is of a Sn-fiber-wound Si particle composite structure and composed of two elements Si and Sn, wherein the Si content is 20-70at.% and the balance is Sn. According to the preparation method of the composite anode material, Si and Sn powder are mixed and the mixed powder is ball milled by using a high-energy ball milling method in an argon atmosphere; under the action of high-energy impact, metal Sn particles deform seriously, are subjected to cold welding and torn to form Sn fibers; through further ball milling, fiber-structured ductile-phase metal Sn formed after high-energy ball milling and Si particles smashed under high-energy impact in the ball milling process are composited to form a Sn-fiber-wound Si particle composite structure. The novel Sn-fiber-wound Si composite material is simple in preparation process and low in cost; in addition, the composite material is novel and unique in structure and excellent in electrochemical performance and therefore has excellent application prospect.

Description

A kind of silicon-tin composite material for lithium ion battery negative and preparation method thereof
Technical field
The present invention relates to electrochemical power source technical field, be specifically related to the composite material containing silicon for lithium ion battery, a kind of siliceous Filament-wound Machine coated lithium ion battery composite material and preparation method thereof is provided especially.
Background technology
Lithium ion battery is the feature such as volume is little, quality is light, specific energy is high, long service life, output voltage are high, self discharge is low, environmental friendliness and be called 21 century optimal green energy resource owing to having, and has been widely used as the energy reserves system of space flight, military affairs, auto industry, electronic equipment and biomedical sector.But, current commercial Li-ion battery mainly adopts carbon materials (such as carbon, graphite etc.) as negative pole, its theoretical embedding lithium capacity is 372mAh/g, is difficult to meet large-scale electric energy supply unit and electric automobile, hybrid vehicle to the requirement of lithium ion cell high-capacity and high-energy-density.For this reason, the continuous effort of vast researcher, attempts to find the Novel anode material system that can substitute carbon materials.
Report much promising new material in recent years, wherein silicon materials receive much concern owing to having huge lithium storage content.Silicon is little because having atomic weight, and specific capacity is high (forms Li in theory 22si 5specific capacity reach 4200mAh/g), advantages such as intercalation potential is low and cause the extensive concern of researcher.But up to now, be that its commercialization process of lithium ion battery of negative pole is obstructed with silicon materials, enter commodity market not yet comprehensively, a main cause is, in charge and discharge process, along with embedding and the deintercalation of lithium ion, huge change in volume (more than 300%) can be there is in silicium cathode material, the mechanical disintegration of negative material (cracked and efflorescence) can be caused, and then cause the avalanche of electrode structure, peeling off of electrode material and make electrode material and collector lose electrical contact, thus cause capacity rapid attenuation, cycle performance declines rapidly, finally cause electrode failure.
For the problem of the volumetric expansion that silicon materials exist in charge and discharge process, the solution that current researcher proposes mainly includes: the structure 1) changing material, is prepared into the material of different-shape.Such as, wire, film-form, cellular, nucleocapsid shape etc.Research shows, the silicium cathode silicon materials of these different structure patterns, in charge and discharge process, can effectively reduce Volumetric expansion, and capacity and cycle performance are all greatly improved; 2) silicon and activity/nonactive compound system is synthesized.In compound system, utilize " cushioning frame " to compensate the expansion of silicon materials, make it keep good electrical contact.But in the preparation of composite material, often use the preparation method such as electrochemical deposition and magnetron sputtering, these preparation method's complex process, production efficiency is low, and preparation cost is higher, is difficult to realize large-scale industrial production.
Summary of the invention
The object of the present invention is to provide a kind of novel silicon-tin composite material for lithium ion battery negative and preparation method thereof.Utilize technological operation simple, the high-energy ball milling method that production cost is low prepares novel structure, uniqueness, the composite material of electrochemical performance.Under its general principle is to utilize high energy impact condition, ductile metal tin generation cold welding with tear and form threadiness, and with in mechanical milling process after high energy impact the silicon grain of dispersion and fining carry out compound, silicon grain part is attached on fibrous tin, part be wound around by fibrous tin parcel, obtain Filament-wound Machine coated composite material.Preparation method's technological operation of high-energy ball milling is simple, cost is low.
Technical scheme of the present invention is as follows:
For novel silicon-tin composite material of lithium ion battery negative, this composite material is made up of together elemental silicon, elemental tin; Wherein: by atomic percentage conc, silicone content is 20-70at.%, and surplus is tin.Described silicon-tin composite material, the preferred 50at.% of silicone content.
In described composite material, tin be threadiness, the 3 D stereo winding-type structure that this processbearing astrocyte is open, part silicon grain is attached on fiber, part be wound around by fibrous tin parcel, the size of silicon grain is 10-20 μm.
A kind of preparation method of the novel silicon-tin composite material for lithium ion battery negative; the method is that silica flour, glass putty are mixed (atomic percentage conc: silicon 20-70at.% in required ratio; preferred 50at.%; surplus is glass putty); then under argon gas atmosphere protection, high-energy ball milling is carried out; Ball-milling Time is 1-30 hour, then obtains composite material.Wherein the particle size distribution scope of silicon grain is 10-20 μm.
In described Process During High Energy Ball Milling, the mass ratio of abrading-ball and mixed-powder (silica flour and glass putty) is 5-20:1 (preferred 16:1).
In the present invention, the specification of raw materials is as follows:
Silica flour purity >=99.99%, granule size 20-30 μm; Glass putty purity >=99.5%, granule size 20-30 μm.
Described composite material is prepared into cathode pole piece, and carries out half-cell assembling in glove box, then electrochemical property test is carried out to half-cell.
Compared with existing siliceous cell negative electrode material and preparation method thereof, the present invention has following feature:
1. in siliceous Filament-wound Machine coated lithium ion battery composite material of the present invention, toughness phase metallic tin after ball milling is in threadiness, and with ball milling after the silicon grain compound of dispersion and fining, part silicon grain is attached on tin fiber, part silicon grain, by tin fibers encapsulation, forms open 3 D stereo and is wound around coated structure.
2. metallic tin belongs to lithiated active metal, and its theoretical embedding lithium capacity is 992mAh/g, and higher than carbon materials, significantly can not reduce the overall specific capacity of composite material with silicon compound, the silicon-tin composite material of preparation still can keep high specific capacity.
3. silicon-tin composite material of the present invention, in its tin Filament-wound Machine silicon grain composite construction, part silicon grain is attached on tin fiber, part silicon grain wrap up by tin fiber.This composite construction effectively improves the toughness of material, and in charge and discharge process, silicon grain, after embedding lithium, volumetric expansion occurs, but due to by tin fibers encapsulation, can effectively stop its cracking destruction, thus keep the electrical contact stable with collector, improve cycle performance, improve battery cycle life.
4. the intrinsic conductivity of metallic tin is higher than semiconductor silicon and conventional carbon materials, contribute to electrode material in charge and discharge process, the transmission of lithium ion, the negative pole polarization that this kind of composite material can effectively prevent lithium ion from causing in the deposition on negative material surface, improves the high rate performance of negative material.
5., in silicon-tin composite material described in, silicon is different to lithium current potential from tin, can be formed in the removal lithium embedded under different potentials.Each other as the resilient coating of Stress Release, the stress alleviated in charge and discharge process is concentrated, and reduces the mechanical stress that bulk effect causes, and prevents active material avalanche because excessive stress concentrates, improves the cycle life of negative material further.
6. the preparation method that the present invention relates to is simple to operate, and production cost is low, technology maturation, and can put into production without the need to substantial contribution, Technical investment, industrialization is comparatively easy.The preparation method of this kind of composite material containing silicon has huge application prospect in the commercial process of lithium ion battery negative material.
Accompanying drawing explanation
Fig. 1 is the siliceous (composition: Si prepared 50sn 50) the microscopic appearance SEM of Filament-wound Machine coated composite material schemes
Fig. 2 (a), be siliceous (composition: Si 50sn 50) Filament-wound Machine coated composite material microstructure SEM figure; (b), for corresponding fiber EDS analyze collection of illustrative plates.
Fig. 3 is with siliceous (composition: Si 50sn 50) Filament-wound Machine coated composite material is that active material prepares electrode, is the charging and discharging capacity-voltage pattern to electrode assembling battery with lithium metal.
Fig. 4 is the Si preparing gained under different Ball-milling Time condition 50sn 50the XRD of composite material contrasts collection of illustrative plates.Selected sample is 1 hour, 10 hours, 15 hours, 19 hours, 20 hours, 26 hours, 30 hours.
Fig. 5 is the Si preparing gained under different Ball-milling Time condition 50sn 50the microscopic appearance SEM comparison diagram of composite material.Selected sample be (a), 1 hour, (b), 10 hours, (c), 15 hours, (e), 20 hours, (f), 25 hours.
Fig. 6 is the Si preparing gained under different Ball-milling Time condition 50sn 50the cycle performance comparison diagram of composite material.Selected sample is 1 hour, 10 hours, 15 hours, 20 hours, 25 hours.
Fig. 7 is the Si preparing gained under different Ball-milling Time condition 50sn 50the high rate performance comparison diagram of composite material.Selected sample is 15 hours, 20 hours, 25 hours.
Fig. 8 is heterogeneity, prepares the XRD collection of illustrative plates of gained composite material containing silicon under the ball milling condition of 20 hours.
Fig. 9 is heterogeneity, prepares the charge-discharge performance figure of gained composite material containing silicon under the ball milling condition of 20 hours.
Embodiment
Below in conjunction with drawings and Examples in detail the present invention is described in detail.By the description of embodiment and comparative example, set forth substantive distinguishing features of the present invention and advantage further.For convenience of description, first preparation method and the test process of material is illustrated by embodiment 1, and structure and the performance characteristics of material in the present invention are described by microstructure observing and performance test, then described by comparative example 1, the novelty of uniqueness with structure of preparation method is described.And then enforcement 2-6 is described, corresponding effect is described.
Embodiment 1
High-energy ball milling method is utilized to prepare Si 50sn 50filament-wound Machine coated composite material, and carry out electrochemical property test as lithium ion battery negative material.
1. for nominal composition Si 50sn 50atomic percent, wherein the atomic percent of element silicon is 50at.%, and the atomic percent of tin element is 50at.%, to meet in technical scheme between required Composition Region.
2. (silicon: 50at.%, tin: 50at.%) mixing of selected raw material silica flour and glass putty proportionally being prepared burden is rear to be loaded in the supporting ball grinder of ball-grinding machine.In the present embodiment, high-energy ball milling selects bearing steel ball, and diameter comprises 10mm, 8mm and 5mm tri-kinds of specifications, and the mass ratio of ball and mixed-powder is 16:1.Under argon atmosphere, carry out ball milling, rotational speed of ball-mill is 250rpm.Si is obtained after high-energy ball milling through 20 hours 50sn 50filament-wound Machine coated composite material, this composite material is containing a large amount of fiber and particle, and bandwidth is about 10 μm, and thick about 2 μm, granular size is about 10-20 μm.Fig. 1 is Si 50sn 50the microscopic appearance SEM of Filament-wound Machine coated composite material schemes; Fig. 2 is that the energy spectrum analysis EDS of the fiber of microstructure and correspondence schemes.Due to the cold welding under high energy impact and tear effect, produce a large amount of fibrous materials, particle is by dispersion and fining simultaneously, and can see in EDS figure, the fibrous material of formation is toughness phase metallic tin.
3. the assembling of battery and performance test: obtain Si 50sn 50after Filament-wound Machine coated composite material, use it as active material, in 1-METHYLPYRROLIDONE (NMP) medium, slurry is made according to the mass ratio of 40:40:20 with conductive carbon black (Super-P) and polyvinylidene fluoride (PVDF), to be coated on Copper Foil and at 120 DEG C, vacuum dry 12 hours, to make negative electrode film thus.Again using lithium metal as to electrode, 25 μm of U.S. celgard are barrier film, 1molLiPF 6/ (PC+DMC) (1:1) is electrolyte, in glove box, carry out battery assembling, and glove box controls water content at below 0.1ppm.Under various conditions charge-discharge performance test is carried out to the battery assembled.Fig. 3 is Si 50sn 50filament-wound Machine coated composite material charging and discharging curve figure, therefrom can find out that this material electrochemical performance is excellent, discharge capacity reaches 1380mAh/g first, still remains on 1000mAh/g after 50 circulations.
Comparative example 1
The Si under different Ball-milling Time is prepared respectively by high-energy ball milling method 50sn 50composite material contrasts, and will prepare the Si of gained according to the mode of embodiment 1 50sn 50composite material makes cathode pole piece respectively as active material, is assembled into battery.And charge-discharge test is carried out under the condition of 0.1C, test voltage scope is 0.03-1.5V.
The Si of gained is prepared under Figure 4 shows that different Ball-milling Time condition 50sn 50the XRD of composite material contrasts collection of illustrative plates, and selected sample is 1 hour, 10 hours, 15 hours, 19 hours, 20 hours, 26 hours, 30 hours.As can see from Figure 4 along with the growth of Ball-milling Time, the intensity of diffraction maximum changes, occur by by force to weak again to strong Changing Pattern, ball milling prepares the Si of gained for 20 hours under condition 50sn 50its XRD diffraction peak intensity of composite material is minimum.Can infer thus, be milled to 20 hours, the structural change degree of material is maximum.Meanwhile, on XRD collection of illustrative plates, there is not the diffraction maximum of the nonactive phases such as the oxide of silicon, illustrate that in mechanical milling process, inert gas shielding is reasonable, can not introduce and be mingled with, be conducive to ensureing high embedding lithium specific capacity.
The Si of gained is prepared under Figure 5 shows that different Ball-milling Time condition 50sn 50the microscopic appearance SEM comparison diagram of composite material, selected sample is 1 hour, 10 hours, 15 hours, 20 hours, 25 hours.Can obtain from Fig. 5, in mechanical milling process, along with cold welding and constantly carrying out of tearing, tin fiber increases, and is milled to the Si of 20 hours 50sn 50in composite material, tin fiber content is maximum, obtains ideal Filament-wound Machine coated structure.Can reunite after ball milling was more than 20 hours, form a large amount of cluster bodies.
The Si of gained is prepared under Figure 6 shows that different Ball-milling Time condition 50sn 50the cycle performance comparison diagram of composite material, have chosen in experiment, 1 hour, 10 hours, 15 hours, 20 hours, and the sample of 25 hours carries out cycle performance test.As we can see from the figure, ball milling has the Si of optimal fiber winding type filtering structure for 20 hours 50sn 50composite material is compared to the Si under other different Ball-milling Time conditions 50sn 50composite material, cycle performance is better, has higher capability retention under same loop number of times.
Fig. 7 is the Si preparing gained under different Ball-milling Time condition 50sn 50the high rate performance comparison diagram of composite material, have chosen 15 hours in experiment, 20 hours, and the sample of 25 hours carries out high rate performance contrast test.Test condition is: charging/discharging voltage scope 0.03-1.5V, first under the multiplying power of 0.1C, carry out discharge and recharge 10 circulation, then discharge and recharge 10 circulation under 0.5C multiplying power, then in rate charge-discharge 10 circulation of 1C, returns discharge and recharge 10 circulation under the multiplying power of 0.1C.As can be seen from Figure 7, this electrode carries out discharge and recharge under the multiplying power of 0.1C, 10 be circulated throughout after, specific capacity remains on 1000mAh/g, when charge-discharge magnification is increased to 0.5C, 10 be circulated throughout after, specific capacity remains on 750mAh/g, when charge-discharge magnification rises to 1C, after 10 circulations, specific capacity remains on 700mAh/g, when charge-discharge magnification gets back to 0.1C, after 10 circulations, its specific capacity remains on 980mAh/g.The Si with desirable winding coated structure that ball milling obtained after 20 hours is described 50sn 50composite material has good high rate performance, can keep higher specific capacity under the condition of high current charge-discharge.
Preparation and property in conjunction with composite material in comparative example 1 is tested, and can draw, adds ductile metal phase tin and silicon compound, obtains the Si being wound around coated structure after ball milling 50sn 50composite material is novel structure not only, and its chemical property also exists advantage.
Embodiment 2
High-energy ball milling method is utilized to prepare Filament-wound Machine coated Si under the ball milling condition of 20 hours 20sn 80composite material, and carry out electrochemical property test as lithium ion battery negative material.Difference from Example 1 is: in composition proportion, adopt different ratios.Preparation method and test process are with embodiment 1.
The present embodiment prepares the siliceous Filament-wound Machine coated Si of gained 20sn 80composite material, wherein the content of element silicon is 20at.%, and tin element content is 80at.%, and as shown in Figure 8, silicon and tin are that the form of elemental exists to its XRD collection of illustrative plates.In this composite material containing silicon, fibre structure content is less, and particle size is about 20-30 μm.As shown in Figure 9, for discharge capacity is 1050mAh/g first, after 20 circulations, capacity remains on 350mAh/g to charge-discharge performance test result.
Embodiment 3
High-energy ball milling method is utilized to prepare Filament-wound Machine coated Si under the ball milling condition of 20 hours 30sn 70composite material, and carry out electrochemical property test as lithium ion battery negative material.Difference from Example 1 is: in composition proportion, adopt different ratios.Preparation method and test process are with embodiment 1.
The present embodiment prepares the siliceous Filament-wound Machine coated Si of gained 30sn 70composite material, wherein the content of element silicon is 30at.%, and tin element content is 70at.%, and as shown in Figure 8, silicon and tin are that the form of elemental exists to its XRD collection of illustrative plates.In this composite material containing silicon, fibre structure content is less, and particle size is about 20-30 μm.As shown in Figure 9, for discharge capacity is 1300mAh/g first, after 20 circulations, capacity remains on 600mAh/g to charge-discharge performance test result.
Embodiment 4
High-energy ball milling method is utilized to prepare Filament-wound Machine coated Si under the ball milling condition of 20 hours 40sn 60composite material, and carry out electrochemical property test as lithium ion battery negative material.Difference from Example 1 is: in composition proportion, adopt different ratios.Preparation method and test process are with embodiment 1.
The present embodiment prepares the siliceous Filament-wound Machine coated Si of gained 40sn 60composite material, wherein the content of element silicon is 40at.%, and tin element content is 60at.%, and as shown in Figure 8, silicon and tin are that the form of elemental exists to its XRD collection of illustrative plates.In this composite material containing silicon, fibre structure content is less, and particle size is about 20-30 μm.As shown in Figure 9, for discharge capacity is 1400mAh/g first, after 20 circulations, capacity remains on 500mAh/g to charge-discharge performance test result.
Embodiment 5
High-energy ball milling method is utilized to prepare Filament-wound Machine coated Si under the ball milling condition of 20 hours 60sn 40composite material, and carry out electrochemical property test as lithium ion battery negative material.Difference from Example 1 is: in composition proportion, adopt different ratios.Preparation method and test process are with embodiment 1.
The present embodiment prepares the siliceous Filament-wound Machine coated Si of gained 60sn 40composite material, wherein the content of element silicon is 60at.%, and tin element content is 40at.%, and as shown in Figure 8, silicon and tin are that the form of elemental exists to its XRD collection of illustrative plates.In this composite material containing silicon, fibre structure content is less, and particle size is about 20-30 μm.As shown in Figure 9, for discharge capacity is 1400mAh/g first, after 20 circulations, capacity remains on 700mAh/g to charge-discharge performance test result.
Embodiment 6
High-energy ball milling method is utilized to prepare Filament-wound Machine coated Si under the ball milling condition of 20 hours 70sn 30composite material, and carry out electrochemical property test as lithium ion battery negative material.Difference from Example 1 is: in composition proportion, adopt different ratios.Preparation method and test process are with embodiment 1.
The present embodiment prepares the siliceous Filament-wound Machine coated Si of gained 70sn 30composite material, wherein the content of element silicon is 70at.%, and tin element content is 30at.%, and as shown in Figure 8, silicon and tin are that the form of elemental exists to its XRD collection of illustrative plates.In this composite material containing silicon, fibre structure content is less, and particle size is about 20-30 μm.As shown in Figure 9, for discharge capacity is 1600mAh/g first, after 20 circulations, capacity remains on 350mAh/g to charge-discharge performance test result.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to Spirit Essence of the present invention change or modify, and all should be encompassed within protection scope of the present invention.

Claims (7)

1. for silicon-tin composite material of lithium ion battery negative, it is characterized in that: this anode material is tin Filament-wound Machine silicon grain composite construction, be made up of silicon, tin two kinds of elements, wherein silicone content is 20-70at.%, and surplus is tin.
2. according to silicon-tin composite material according to claim 1, it is characterized in that: in this composite material, metallic tin is threadiness, and form open 3 D stereo winding arrangement, in described composite material, silicon grain part is attached on fibrous tin, part be wound around by fibrous tin parcel; The particle size of silicon grain is 10-20 μm.
3. a preparation method for silicon-tin composite material described in claim 1, is characterized in that: the method is mixed in required ratio silica flour and glass putty, then prepares described composite material by high-energy ball milling method.
4. according to the preparation method of silicon-tin composite material described in claim 3, it is characterized in that: in described high-energy ball milling method, the mass ratio of abrading-ball and mixed powder is 5-20:1.
5. according to the preparation method of silicon-tin composite material described in claim 3, it is characterized in that: described high-energy ball milling carries out under argon gas atmosphere protection.
6. according to the preparation method of silicon-tin composite material described in claim 3, it is characterized in that: the time of described high-energy ball milling is 1-30 hour.
7. according to the preparation method of silicon-tin composite material described in claim 3, it is characterized in that: silica flour purity >=99.99% in raw material, granule size 20-30 μm; Glass putty purity >=99.5%, granule size 20-30 μm.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106848182A (en) * 2017-01-12 2017-06-13 深圳市沃特玛电池有限公司 A kind of preparation method of lithium ion battery negative electrode
CN109585834A (en) * 2018-12-10 2019-04-05 包头市石墨烯材料研究院有限责任公司 A kind of mesoporous silicon-tin composite electrode material and its preparation method and application
CN111987295A (en) * 2019-05-24 2020-11-24 南京大学 Silicon composite material and preparation and application thereof
RU2810105C1 (en) * 2022-01-04 2023-12-21 Пролоджиум Текнолоджи Ко., Лтд. Composite ball of active material negative electrode

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103280555A (en) * 2013-01-21 2013-09-04 深圳大学 Lithium ion battery silicon-based alloy cathode material and preparation method thereof and lithium ion battery
CN103647061A (en) * 2013-11-15 2014-03-19 成都兴能新材料有限公司 Preparation method of silicon-based alloy cathode material
CN104282897A (en) * 2013-07-10 2015-01-14 中国科学院金属研究所 Silicon-based nanometer composite anode material for lithium ion battery and preparation method of silicon-based nanometer composite anode material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103280555A (en) * 2013-01-21 2013-09-04 深圳大学 Lithium ion battery silicon-based alloy cathode material and preparation method thereof and lithium ion battery
CN104282897A (en) * 2013-07-10 2015-01-14 中国科学院金属研究所 Silicon-based nanometer composite anode material for lithium ion battery and preparation method of silicon-based nanometer composite anode material
CN103647061A (en) * 2013-11-15 2014-03-19 成都兴能新材料有限公司 Preparation method of silicon-based alloy cathode material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106848182A (en) * 2017-01-12 2017-06-13 深圳市沃特玛电池有限公司 A kind of preparation method of lithium ion battery negative electrode
CN109585834A (en) * 2018-12-10 2019-04-05 包头市石墨烯材料研究院有限责任公司 A kind of mesoporous silicon-tin composite electrode material and its preparation method and application
CN111987295A (en) * 2019-05-24 2020-11-24 南京大学 Silicon composite material and preparation and application thereof
RU2810105C1 (en) * 2022-01-04 2023-12-21 Пролоджиум Текнолоджи Ко., Лтд. Composite ball of active material negative electrode

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