CN110148730A - A kind of Gao Shouxiao long-life silicon based anode material and its preparation method and application - Google Patents

A kind of Gao Shouxiao long-life silicon based anode material and its preparation method and application Download PDF

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CN110148730A
CN110148730A CN201910453138.XA CN201910453138A CN110148730A CN 110148730 A CN110148730 A CN 110148730A CN 201910453138 A CN201910453138 A CN 201910453138A CN 110148730 A CN110148730 A CN 110148730A
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preparation
sio
based anode
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silicon based
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CN110148730B (en
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王辉
王庆莉
林少雄
周勇岐
许家齐
陈龙
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/626Metals
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of Gao Shouxiao long-life silicon based anode materials and its preparation method and application to make SiO that the Si/SiO that disproportionated reaction obtains relatively uniform silicon wafer particle size occur by high temperature pre-treatment2Material, then in CO2Na restores part SiO under atmosphere2Material coulombic efficiency for the first time is improved, CO is selected2SiO can be reduced as reaction gas2The gibbs free energy change reacted with Na carries out reaction quickly under the conditions of relatively mild.The carbon coating layer for being formed by chemical vapor deposition even compact improves the electronic conductivity of material, reduces material resistance.Secondary conducting polymer cladding improves the interface performance of material, further increases the cyclical stability of material.And the poor defect of improvement polymer conductivity is modified by high conductivity nano-metal particle.Lithium ion battery made of material prepared by the present invention, the specific capacity of battery, for the first time coulombic efficiency and cyclical stability are improved, and have fabulous application prospect.

Description

A kind of Gao Shouxiao long-life silicon based anode material and its preparation method and application
Technical field
The present invention relates to a kind of lithium ion battery material more particularly to a kind of Gao Shouxiao long-life silicon based anode materials And its preparation method and application.
Background technique
With the development of electric car and portable electrical appliance, the demand of lithium ion battery with high energy density also increasingly increases Add.Conventional graphite negative material theoretical specific capacity only has 372mAh/g, is difficult to meet the market demand.The gram volume for the first time of silicon materials For 4200mAh/g, embedding lithium platform is higher, and earth's crust storage is abundant, and the advantages such as environmentally friendly gradually cause the extensive pass of researcher Note.
However the volume expansion of silicon is up to 300%, in cyclic process, not only results in the conductive charcoal network of silicon and surrounding Separation forms " dead silicon ", it is peeling-off with collector to also result in silicon.Secondly, biggish volume expansion also results in surface SEI film constantly recombinates destruction, keeps SEI film more and more thicker, constantly the Li of consumption anode+, coulombic efficiency reduction.Finally, biggish The phase leads to silicon materials dusting after cycling for volume expansion, and these problems eventually lead to cycle performance and sharply deteriorate.
Due to the above problem, part attention is transferred on the sub- silicon of oxidation by academia and industrial circle.Compared with nano-silicon, It aoxidizes sub- silicon and although sacrifices portion capacity, but its expansion is relatively small (~100%), and generated in charge and discharge process By-product lithia, lithium metasilicate, lithium metasilicate etc. can provide buffer function, greatly improve the cycle performance of material.But The electric conductivity of material is relatively poor, and head effect is lower.Lee D J[Lee D J,Ryou M H,Lee J N,et al.Nitrogen-doped carbon coating for a high-performance SiO anode in lithium- Ion batteries [J] .Electrochemistry Communications, 2013,34:98-101.] etc. it is mixed by liquid phase Conjunction+high temperature cabonization mode prepares nitrogen-doped carbon coated Si O material, and the material circulation is relatively preferable, but first effect is relatively low.Jee [Yom J H, Sun W H, Cho S M, the et al.Improvement of irreversible behavior of such as HoYom SiO anodes for lithium ion batteries by a solid state reaction at high Temperature [J] .Journal of Power Sources, 2016,311:159-166.] by by SiO and lithium metal into Row solid phase reaction is carrying out carbon coating, is preparing Gao Shouxiao silicon based anode material, the method increase material coulombic efficiency for the first time, But the cycle performance of material is relatively poor, comparatively harsh to synthesis condition due to using lithium metal as reactant, exists Security risk, and there is the risk for producing gas during battery is closed and starched.
Summary of the invention
To overcome defect of the existing technology, the object of the present invention is to provide a kind of Gao Shouxiao long-life silicon-based anode materials Material and its preparation method and application.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of preparation method of Gao Shouxiao long-life silicon based anode material, comprising the following steps:
S1, the sub- silicon of oxidation are calcined under inert gas protection, obtain calcining materials;By high-temperature calcination pre-treatment, SiO occurs disproportionated reaction and obtains the Si/SiO for having relatively uniform silicon wafer particle size2Material.
S2, calcining materials and metal Na after mixing, in CO2Reduction reaction is carried out in atmosphere, obtains reducing material;? CO2Part SiO is heat-treated by Na under atmosphere2, improve the coulombic efficiency for the first time of material, and the remaining SiO not being reduced2 Material circulation stability can be improved with the volume expansion of padded coaming.CO2SiO can be reduced as reaction gas2It is reacted with Na Gibbs free energy change, make reaction quickly carried out under the conditions of relatively mild.
S3, reducing material are after pickling impurity removal, then wash to neutrality, obtain dried material after dry;Acid processing is main Remove the Na of unreacted Na and reaction generation2O and Na2CO3Deng.
S4, dried material is placed in inert gas, is passed through cracking performance gas and carries out chemical vapor deposition, obtains carbon coating Material;The cladding carbon-coating even compact being prepared by chemical vapor deposition, can significantly improve the electronic conductivity of material;
S5, carbon encapsulated material is dispersed in deionization water-alcohol system, surfactant, high conductivity nanogold is added Category and polymer monomer are simultaneously uniformly mixed, and initiator is then added and carries out auto polymerization reaction, obtains conducting polymer packet after drying Cover material;By coating one layer of conducting polymer in material outer layer, improves the interface performance of material, further increase material circulation Performance;In addition, overcoming the relatively poor (phase of conducting polymer performance by the way that high conductivity nano metal is added in the polymer For carbon material) defect, further increase the electron conduction of material, improve the coulombic efficiency for the first time and circulation of material Service life.
S6, it after conducting polymer covering material is broken into powdery granule, is mixed with graphite and obtains high first effect longevity Order silicon based anode material.Since graphite electronic conductivity is higher, matter is soft, can further buffer the volume expansion of silica-base material, Therefore it is mixed by demand to obtain the silicon based anode material of Gao Shouxiao long-life.
Further, in step sl, the median particle diameter for aoxidizing sub- silicon is 5 μm~7 μm;The inert gas is helium At least one of gas, neon, argon gas, Krypton, xenon;The calcining is carried out in rotary furnace, and the rotary furnace turns Speed is 0.25r/min~1r/min;The temperature of the calcining is 800 DEG C~1200 DEG C, and the time is 0.5h~6h.With other sintering Equipment is compared, and revolution furnace temperature is more uniform.
Further, in step s 2, the calcining materials, metal Na and CO2Molar ratio be 2:(4~1): 1;CO2It rubs You are calculated with gas flow rate multiplied by reduction reaction constant temperature time amount;The temperature of reduction reaction is 200 DEG C~800 DEG C, time 1h ~12h.Reduction reaction is carried out in rotary furnace, and rotary furnace revolving speed is 0.25r/min~1r/min.
Further, in step s3, acid used in the pickling is one or more of hydrochloric acid, sulfuric acid, nitric acid, acid Mass fraction be 10%~50%;Pickling time is 0.5h~3h.
Further, in step s 4, the volume ratio of the inert gas and cracking performance gas is 5:1~1:1, chemical gas Mutually the time of deposition is 0.5h~6h, and chemical vapor deposition is carried out in rotary furnace, and the revolving speed of the rotary furnace is 0.25r/min~1r/min;The cracking performance gas is methane or its homologue, acetylene or its homologue, benzene or its homologue At least one of,
Further, in step s 5, the deionization water-alcohol system be deionization water-methanol, deionization water-ethanol, One kind of deionized water-propyl alcohol, deionized water-isopropanol and deionization water-methanol;The surfactant is polyethylene pyrrole At least one of pyrrolidone, lauryl sodium sulfate or neopelex;The high conductivity nano metal be Ag, At least one of Au, Cu, the median particle diameter of the high conductivity nano metal are 10nm~200nm;The polymer monomer For at least one of pyrroles, dopamine, acrylonitrile or aniline;The initiator is hydrogen peroxide, iron chloride or ammonium persulfate At least one of.The addition of surfactant can improve the compatibility between material and polymer monomer, promote reaction It carries out.
Further, in step s 6, the broken median particle diameter of conducting polymer covering material is 5 μm~7 μm, The mass fraction that the graphite accounts for Gao Shouxiao long-life silicon based anode material is 0%~95%.
Further, in step s 6, the graphite be natural graphite, it is artificial graphite, carbonaceous mesophase spherules, hard carbon, soft At least one of carbon, the median particle diameter of the graphite are 10 μm~20 μm.
It is another object of the present invention to provide the Gao Shouxiao long-life silicon-based anodes as made from above-mentioned preparation method Material.
Third object of the present invention is to provide above-mentioned Gao Shouxiao long-life silicon based anode material in lithium ion battery Application.Silica-base material of the invention is prepared into lithium ion battery as negative electrode material, electricity is carried out to lithium ion battery obtained The test of chemical property, the specific capacity of lithium ion battery obtained, first effect and cyclical stability are improved.
Compared with prior art, the invention has the benefit that
(1) present invention, first by high temperature pre-treatment, makes SiO that disproportionated reaction acquisition occur relatively equal using SiO as raw material The Si/SiO of even silicon wafer particle size2Material, then in CO2Na restores part SiO under atmosphere2Improve material coulombic efficiency for the first time, The SiO that residue is not reduced2Material circulation stability can be improved with the volume expansion of padded coaming.Select CO2As reaction gas Body can reduce SiO2The gibbs free energy change reacted with Na carries out reaction quickly under the conditions of relatively mild.It is aided with again The carbon coating layer that chemical vapor deposition (CVD) forms even compact improves the electronic conductivity of material, reduces material resistance.Pass through Secondary conducting polymer cladding improves the interface performance of material, further increases the cyclical stability of material.The present invention utilizes stone The properties such as black electronic conductivity is higher, and matter is soft mix it with silica-base material, so as to further buffer the body of silica-base material Product expansion, is prepared Gao Shouxiao long-life silicon based anode material.
(2) high conductivity nano metal is added in the experiment for preparing secondary conducting polymer covering material in the present invention, with Improve the polymer conductivity defect poor compared with carbon material, further increases the electron conduction of material, improve material for the first time Coulombic efficiency and cycle life.And simple process, it is easy to amplify production.
(3) lithium ion battery is made using material prepared by the present invention as negative electrode material, to lithium ion battery obtained into The test of row chemical property, the specific capacity of lithium ion battery obtained, for the first time coulombic efficiency and cyclical stability are mentioned Height has fabulous application prospect.
Detailed description of the invention
Fig. 1 is the SEM figure of silicon based anode material prepared by embodiment 1;
Fig. 2 is first charge-discharge of the battery under 0.1C current density made of the material of embodiment 1 and the preparation of comparative example 1 Curve;
Fig. 3 is first charge-discharge of the battery under 0.1C current density made of the material of embodiment 2 and the preparation of comparative example 2 Curve;
Fig. 4 is full battery of the battery under 1C/1C current density made of the material of embodiment 2 and the preparation of comparative example 2 Cycle performance curve.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention will be further explained.Obviously, described embodiment is this Invention a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art exist Every other embodiment obtained under the premise of creative work is not made, shall fall within the protection scope of the present invention.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention Protection scope.
Except there is a special instruction, the various reagents used in the present invention, raw material be can commodity commercially or Person can the product as made from well known method.
Embodiment 1
3kg SiO is placed in the rotary furnace under argon atmosphere protection, 800 DEG C of processing 6h are warming up to 10 DEG C/min, it should In the process, furnace body keeps 0.25r/min, and room temperature discharges to obtain calcining materials.Then by calcining materials, metal Na according to 2:4's Ratio is uniformly mixed, and is subsequently added to CO2In rotary furnace under atmosphere protection, 10 DEG C/min is warming up to 600 DEG C of processing 6h (constant temperature Guarantee Na:SiO:CO in the process2Molar ratio is 2:4:1), during being somebody's turn to do, furnace body keeps 0.25r/min, and room temperature discharging is gone back Raw material.Above-mentioned reducing material is placed in 10% dilute hydrochloric acid solution, 0.5h is impregnated, is then filtered, and use deionization Water washing filter cake 3 times are neutrality to filtrate PH, are then dried in 60 DEG C of dryings.Take the dry complete material of 3kg It is placed in the rotary furnace under argon atmosphere protection, is warming up to 800 DEG C with 10 DEG C/min, flow velocity is according to argon gas at this time: acetylene=5:1 Ratio be passed through acetylene and argon gas, react 6h, then stop being passed through acetylene, argon gas flow velocity is constant, in entire sintering process In, furnace body revolving speed keeps 0.25r/min, room temperature discharging.Take above-mentioned product 1.95kg, 0.05kg copper nanoparticle (10nm) and 200mL pyrroles's (Py) monomer and 0.02kg polyvinylpyrrolidone are dispersed in 5L deionization water-ethanol, are slowly added dropwise Enter the FeCl of 3L 0.5mol/L3Solution carries out polymerization reaction 2h, then carries out washing drying.Material after drying is placed in machine It in tool mill, is crushed and carries out de-agglomerated, obtain the silicon based anode material that D50 is 6 μm.
Fig. 1 is the SEM figure of silicon based anode material prepared by embodiment 1, it is found that granular size is comparatively uniform, About 6 μm of particle or so.By the silicon based anode material of preparation: SP:LA133=8:1:1 ratio carries out conjunction slurry, coating, assembling CR2016 button cell, electrolyte use 1mol/L LiPF6EC+DMC solution, and carry out electrochemical property test.As a result such as Shown in Fig. 2, under the current density of 0.1C, the first discharge specific capacity of battery made of material prepared by embodiment 1 is 1754mAh/g, charge specific capacity 1486mAh/g, coulombic efficiency is 84.7% for the first time.
Comparative example 1
By commercialized SiO/C material: SP:LA133=8:1:1 ratio carries out conjunction slurry, coating, assembling CR2016 button electricity Pond, electrolyte use 1mol/L LiPF6EC+DMC solution, and carry out electrochemical property test.As a result as shown in Fig. 2, Under 0.1C current density, the first discharge specific capacity of battery made of material prepared by comparative example 1 is 2189mAh/g, charge ratio Capacity is 1593mAh/g, and coulombic efficiency is 72.8% for the first time.It is compared by embodiment 1 and comparative example 1 it can be found that embodiment 1 The coulombic efficiency for the first time of battery made of the material being prepared is greatly improved.
Embodiment 2
3kg SiO is placed in the rotary furnace under neon atmosphere protection, 1200 DEG C of processing 0.5h are warming up to 10 DEG C/min, it should In the process, furnace body keeps 1r/min, and room temperature discharging obtains calcining materials.Then by calcining materials, metal Na according to 2:4 ratio Example is uniformly mixed, and is subsequently added to CO2In rotary furnace under atmosphere protection, 10 DEG C/min is warming up to 200 DEG C of processing 12h (constant temperature Guarantee Na:SiO:CO in the process2Molar ratio is 2:1:1), during being somebody's turn to do, furnace body keeps 1r/min, room temperature discharging.By above-mentioned object Material is placed in 50% dilution heat of sulfuric acid, is impregnated 3h, is then filtered, and filter cake 3 times is washed with deionized to filtrate PH For neutrality, then it is dried in 60 DEG C of dryings.The dry complete material of 3kg is taken to be placed in returning under neon atmosphere protection In converter, be warming up to 1200 DEG C with 10 DEG C/min, flow velocity is according to neon at this time: acetylene=5:1 ratio is passed through acetylene and neon Gas reacts 0.5h, then stops being passed through acetylene, and neon flow velocity is constant, and in entire sintering process, furnace body revolving speed keeps 1r/ Min, room temperature discharging.Take above-mentioned product 1.95kg, 0.05kg copper nanoparticle (10nm) and 200mL pyrroles's (Py) monomer and 0.02kg Neopelex is dispersed in 5L deionization water-ethanol, and the FeCl into 3L 0.5mol/L is slowly added dropwise3Solution Polymerization reaction 2h is carried out, washing drying is then carried out.Material after drying is placed in mechanical mill, is crushed and carries out de-agglomerated, obtain The silicon based anode material that D50 is 6 μm is obtained, the material and artificial graphite are mixed according to the ratio of 1:3, wherein used artificial Graphite D50 is 15 μm, obtains Gao Shouxiao long-life silicon based anode material.
By the Gao Shouxiao long-life silicon based anode material of preparation: SP:LA133=8:1:1 ratio carries out conjunction slurry, coating, group CR2016 button cell is filled, electrolyte uses 1mol/L LiPF6EC+DMC solution, and carry out electrochemical property test, test As a result as shown in figure 3, the first discharge specific capacity of battery made of material prepared by embodiment 2 is 684.6mAh/g, charge ratio Capacity is 604.8mAh/g, and coulombic efficiency is 88.3% for the first time.It is anode with NCM622, material prepared by embodiment 2 is cathode, It is soft that the processes such as conjunction slurry, coating, roll-in, cutting, cross cutting, lamination, welding electrode ear, top side seal, baking, fluid injection assembling 7Ah is carried out respectively Packet battery after forming and capacity dividing, carries out normal temperature circulation test, as a result as shown in figure 4, current full battery under 1C/1C current density Circulation 516 weeks, capacity retention ratio 91.2%.
Comparative example 2
By commercialized SiO/C/ graphite material: SP:LA133=8:1:1 ratio carries out conjunction slurry, coating, assembles CR2016 Button cell, electrolyte use 1mol/L LiPF6EC+DMC solution, and carry out electrochemical property test.As a result such as Fig. 3 institute Show, under 0.1C current density, the first discharge specific capacity of battery made of material prepared by comparative example 2 is 721.2mAh/g, Charge specific capacity is 608.2mAh/g, and coulombic efficiency is 84.3% for the first time.It can be with by embodiment 2 in Fig. 3 and the comparison of comparative example 2 It was found that the coulombic efficiency for the first time of battery made of the material that the present invention is prepared is greatly improved.It is with NCM622 Anode, the commercialization SiO/C/ graphite in comparative example 2 are cathode, carry out respectively conjunction slurry, coating, roll-in, cutting, cross cutting, lamination, The processes such as welding electrode ear, top side seal, baking, fluid injection assemble 7Ah soft-package battery, after forming and capacity dividing, carry out under 1C/1C current density Normal temperature circulation test, as a result as shown in figure 4, full battery recycles 516 weeks at present, capacity retention ratio 85.7%.By real in Fig. 4 Apply example 2 and comparative example 2 comparison it can be found that material by polymer overmold and high conductivity nano-metal particle modification after, The cycle performance of material promotes about 6%, and stability is improved, this is because polymer overmold can improve the boundary of material Face performance, while the modification of high conductivity nano-metal particle can make up the conducting polymer electric conductivity defect poor compared with carbon material Reason.
Embodiment 3
3kg SiO is placed in the rotary furnace under argon atmospher protection, 900 DEG C of processing 3h, the mistake are warming up to 10 DEG C/min Cheng Zhong, furnace body keep 0.5r/min, and room temperature discharging obtains calcining materials.Then by calcining materials, metal Na according to 2:4 ratio Example is uniformly mixed, and is subsequently added to CO2In rotary furnace under atmosphere protection, 10 DEG C/min is warming up to 400 DEG C of processing 1h (constant temperature mistakes Guarantee Na:SiO:CO in journey2Molar ratio is 2:2:1), during being somebody's turn to do, furnace body keeps 0.5r/min, room temperature discharging.By above-mentioned object Material is placed in 10% dilute hydrochloric acid solution, is impregnated 0.5h, is then filtered, and filter cake 3 times is washed with deionized to filtrate PH is neutrality, is then dried in 60 DEG C of dryings.The dry complete material of 3kg is taken to be placed under argon atmosphere protection In rotary furnace, be warming up to 900 DEG C with 10 DEG C/min, flow velocity is according to argon gas at this time: methane=5:1 ratio is passed through methane and argon gas Gas reacts 6h, then stops being passed through acetylene, and argon gas flow velocity is constant, and in entire sintering process, furnace body revolving speed keeps 0.5r/ Min, room temperature discharging.Take above-mentioned product 1.95kg, 0.05kg nano-silver powder (100nm) and 200mL aniline (ANi) monomer and 0.02kg lauryl sodium sulfate is dispersed in 5L deionized water-propyl alcohol, and the FeCl into 3L 0.5mol/L is slowly added dropwise3 Solution carries out polymerization reaction 2h, then carries out washing drying.Material after drying is placed in mechanical mill, it is broken to carry out solution group It is poly-, the silicon based anode material that D50 is 5 μm is obtained, the material and carbonaceous mesophase spherules are mixed according to the ratio of 1:2, In artificial graphite D50 used be 10 μm, obtain Gao Shouxiao long-life silicon based anode material.
Embodiment 4
3kg SiO is placed in the rotary furnace under argon atmospher protection, 900 DEG C of processing 3h, the mistake are warming up to 10 DEG C/min Cheng Zhong, furnace body keep 0.5r/min, and room temperature discharging obtains calcining materials.Then by calcining materials, metal Na according to 2:4 ratio Example is uniformly mixed, and is subsequently added to CO2In rotary furnace under atmosphere protection, 10 DEG C/min is warming up to 600 DEG C of processing 4h (constant temperature mistakes Guarantee Na:SiO:CO in journey2Molar ratio is 2:2:1), during being somebody's turn to do, furnace body keeps 0.5r/min, room temperature discharging.By above-mentioned object Material is placed in 10% dilute hydrochloric acid solution, is impregnated 0.5h, is then filtered, and filter cake 3 times is washed with deionized to filtrate PH is neutrality, is then dried in 60 DEG C of dryings.The dry complete material of 3kg is taken to be placed under argon atmosphere protection In rotary furnace, be warming up to 900 DEG C with 10 DEG C/min, flow velocity is according to argon gas at this time: acetylene=5:1 ratio is passed through acetylene and argon gas Gas reacts 6h, then stops being passed through acetylene, and argon gas flow velocity is constant, and in entire sintering process, furnace body revolving speed keeps 0.5r/ Min, room temperature discharging.Take above-mentioned product 1.95kg, 0.05kg nano-gold powder (10nm) and 200mL dopamine (DA) monomer and 0.02kg polyvinylpyrrolidone is dispersed in 5L deionized water-isopropanol, is slowly added dropwise into 5L 0.1M ammonium persulfate Solution carries out polymerization reaction 2h, then carries out washing drying.Material after drying is placed in mechanical mill, it is broken to carry out solution group It is poly-, the silicon based anode material that D50 is 7 μm is obtained, the material and natural graphite are mixed according to the ratio of 1:4, wherein institute It is 20 μm with artificial graphite D50, obtains Gao Shouxiao long-life silicon based anode material.
Embodiment 5
3kg SiO is placed in the rotary furnace under argon atmospher protection, 900 DEG C of processing 3h, the mistake are warming up to 10 DEG C/min Cheng Zhong, furnace body keep 0.5r/min, and room temperature discharging obtains calcining materials.Then by calcining materials, metal Na according to 2:4 ratio Example is uniformly mixed, and is subsequently added to CO2In rotary furnace under atmosphere protection, 10 DEG C/min is warming up to 600 DEG C of processing 12h (constant temperature Guarantee Na:SiO:CO in the process2Molar ratio is 2:4:1), during being somebody's turn to do, furnace body keeps 0.5r/min, room temperature discharging.It will be above-mentioned Material is placed in 10% dilute hydrochloric acid solution, is impregnated 0.5h, is then filtered, and is washed with deionized filter cake 3 times and is extremely filtered Liquid PH is neutrality, is then dried in 60 DEG C of dryings.The dry complete material of 3kg is taken to be placed under argon atmosphere protection Rotary furnace in, be warming up to 900 DEG C with 10 DEG C/min, flow velocity is according to argon gas at this time: acetylene=5:1 ratio is passed through acetylene and argon Gas gas reacts 6h, then stops being passed through acetylene, and argon gas flow velocity is constant, and in entire sintering process, furnace body revolving speed is kept 0.5r/min, room temperature discharging.Take above-mentioned product 1.95kg, 0.05kg copper nanoparticle (10nm) and 200mL dopamine (DA) monomer With with 0.02kg neopelex, be dispersed in 5L deionized water-isopropanol, be slowly added dropwise into 5L mass fraction Polymerization reaction 2h is carried out for 10% hydrogenperoxide steam generator, then carries out washing drying.Material after drying is placed in mechanical mill, It is broken to carry out de-agglomerated, obtain the silicon based anode material that D50 is 7 μm, by the material and natural graphite according to 5:95 ratio into Row mixing obtains Gao Shouxiao long-life silicon based anode material wherein artificial graphite D50 used is 20 μm.

Claims (10)

1. a kind of preparation method of Gao Shouxiao long-life silicon based anode material, it is characterised in that: the following steps are included:
S1, the sub- silicon of oxidation are calcined under inert gas protection, obtain calcining materials;
S2, calcining materials and metal Na after mixing, in CO2Reduction reaction is carried out in atmosphere, obtains reducing material;
After pickling impurity removal, washing to neutrality obtains dried material after dry for S3, reducing material;
S4, dried material is placed in inert gas, is passed through cracking performance gas and carries out chemical vapor deposition, obtains carbon coating material Material;
S5, carbon encapsulated material is dispersed in deionization water-alcohol system, be added surfactant, high conductivity nano metal and Polymer monomer is simultaneously uniformly mixed, and initiator is then added and carries out auto polymerization reaction, and conducting polymer cladding material is obtained after dry Material;
S6, it after conducting polymer covering material is broken into powdery granule, is mixed with graphite and obtains Gao Shouxiao long-life silicon Base negative electrode material.
2. preparation method according to claim 1, it is characterised in that: in step sl, the intermediate value grain for aoxidizing sub- silicon Diameter is 5 μm~7 μm;The inert gas is at least one of helium, neon, argon gas, Krypton, xenon;It is described calcining be It is carried out in rotary furnace, the revolving speed of the rotary furnace is 0.25r/min~1r/min;The temperature of the calcining be 800 DEG C~ 1200 DEG C, the time is 0.5h~6h.
3. preparation method according to claim 1, it is characterised in that: in step s 2, the calcining materials, metal Na with CO2Molar ratio be 2:(4~1): 1;The temperature of the reduction reaction is 200 DEG C~800 DEG C, and the time is 1h~12h, and reduction is anti- Should be carried out in rotary furnace, rotary furnace revolving speed is 0.25r/min~1r/min.
4. preparation method according to claim 1, it is characterised in that: in step s3, acid used in the pickling is salt One or more of acid, sulfuric acid, nitric acid, sour mass fraction are 10%~50%;Pickling time is 0.5h~3h.
5. preparation method according to claim 1, it is characterised in that: in step s 4, the inert gas and cracking performance The volume ratio of gas is 5:1~1:1, and the time of chemical vapor deposition is 0.5h~6h, and chemical vapor deposition is in rotary furnace It carries out, the revolving speed of the rotary furnace is 0.25r/min~1r/min;The cracking performance gas is methane or its homologue, second At least one of alkynes or its homologue, benzene or its homologue.
6. preparation method according to claim 1, it is characterised in that: in step s 5, the deionization water-alcohol system is Deionization water-methanol, deionization water-ethanol, deionized water-propyl alcohol, deionized water-isopropanol and deionization water-methanol It is a kind of;The surfactant be polyvinylpyrrolidone, lauryl sodium sulfate or neopelex at least It is a kind of;The high conductivity nano metal is at least one of Ag, Au, Cu, the intermediate value grain of the high conductivity nano metal Diameter is 10nm~200nm;The polymer monomer is at least one of pyrroles, dopamine, acrylonitrile or aniline;The initiation Agent is at least one of hydrogen peroxide, iron chloride or ammonium persulfate.
7. preparation method according to claim 1, it is characterised in that: in step s 6, the conducting polymer coats material Expect that broken median particle diameter is 5 μm~7 μm, the mass fraction that the graphite accounts for Gao Shouxiao long-life silicon based anode material is 0%~95%.
8. preparation method according to claim 1, it is characterised in that: in step s 6, the graphite is natural graphite, people At least one of graphite, carbonaceous mesophase spherules, hard carbon, soft carbon are made, the median particle diameter of the graphite is 10 μm~20 μm.
9. Gao Shouxiao long-life silicon based anode material made from preparation method a method as claimed in any one of claims 1-8.
10. application of the Gao Shouxiao long-life silicon based anode material as claimed in claim 9 in lithium ion battery.
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