CN108987717A - A kind of lithium ion battery silicon based composite material and preparation method thereof - Google Patents

A kind of lithium ion battery silicon based composite material and preparation method thereof Download PDF

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CN108987717A
CN108987717A CN201810814999.1A CN201810814999A CN108987717A CN 108987717 A CN108987717 A CN 108987717A CN 201810814999 A CN201810814999 A CN 201810814999A CN 108987717 A CN108987717 A CN 108987717A
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silicon
kernel
composite material
product
ion battery
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CN108987717B (en
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刘进
王丽
郝延蔚
赵辉
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Kaifeng University
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Kaifeng University
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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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 present invention relates to a kind of Silicon-carbon composite material for lithium ion battery and preparation method thereof, it is characterised in that the structure of Si-C composite material is class core-shell structure, and class core-shell structure includes kernel and the shell that is coated on outside kernel；Kernel includes the titanium (Ti) and 5%-15% niobium (Nb) of the silicon of 70%-95%, 4%-20%, and silicon is the internal layer of kernel, and titanium (Ti) and niobium (Nb) element are dispersed in the surface of internal layer；Shell is made of graphene and carbon nanotube, and the mass ratio with kernel is 11%-42%, and above-mentioned percentage is mass percent；Using to roller compaction technology in preparation process.It has many advantages, such as high circulation stability, high capacity, can solve silicon-carbon cathode material bulk effect and for the first time low bottleneck problem of discharging efficiency.

Description

A kind of lithium ion battery silicon based composite material and preparation method thereof
Technical field
The invention belongs to novel energy resource material technology field, it is related to a kind of lithium ion battery negative material and preparation method thereof, In particular to a kind of Silicon-carbon composite material for lithium ion battery and preparation method thereof.
Background technique
With the development of lithium ion battery technology, high capacity, small size demand for development be more and more obvious, therefore, exploitation Novel high-capacity negative electrode material is extremely urgent.In numerous candidate materials, silicon materials are because of its higher specific capacity 4200mAh/g And it is concerned.But there are serious volume changes in battery charge and discharge process for pure silicon material, and cause pole piece dusting, It falls off, so that electrode active material and collector is lost electrical contact (and " bulk effect " of material), following for battery can be seriously affected Ring performance.On the other hand, silicon itself is semiconductor material, and conductivity is very low, and these problems hinder silicon based anode material in lithium Large-scale application in ion battery.
In order to solve problem above, researcher has developed multiple technologies means and has been modified raising to silicon materials.At present The method for improving Si material property specifically includes that the nanosizing of Si, porous, the surface Si cladding and doping vario-property and preparation Composite material etc..But silicon-based anode is used for negative electrode of lithium ion battery, there is also actual specific capacities lower, cycle performance is not It is good, there is " bulk effect " and the problems such as discharging efficiency is low for the first time.The nanosizing of silicon is generally considered to can be reduced its volume effect The influence answered, in addition, being also considered as the important channel of solution bulk effect for the volume expansion reserved space of silicon.
Summary of the invention
A kind of Silicon-carbon composite material for lithium ion battery system is provided the purpose of the present invention is overcome the deficiencies in the prior art Preparation Method, the Si-C composite material that this method is prepared have the characteristics that high circulation stability, high capacity, can solve silicon-carbon cathode Material actual specific capacity is lower and the low bottleneck problem of discharging efficiency for the first time.
In order to achieve the above object, Silicon-carbon composite material for lithium ion battery of the invention is achieved in that its feature The structure for being Si-C composite material is class core-shell structure, and class core-shell structure includes kernel and the shell that is coated on outside kernel；It is interior Core includes the titanium (Ti) and 5%-15% niobium (Nb) of the silicon of 70%-95%, 4%-20%, and silicon is the internal layer of kernel, titanium (Ti) and Niobium (Nb) element is dispersed in the surface of internal layer；Shell is made of graphene and carbon nanotube, and the mass ratio with kernel is 11%- 42%, above-mentioned percentage is mass percent.It has the characteristics that high circulation stability, high capacity, can solve silicon-carbon cathode material The advantages that expecting bulk effect and for the first time discharging efficiency low bottleneck problem.
In order to achieve the above object, the preparation method of Silicon-carbon composite material for lithium ion battery of the invention is realized in , it is characterised in that preparation step is as follows: Step 1: collecting the waste silicon powder under Buddha's warrior attendant wire cutting, placing it under inert atmosphere 6-8h is kept in 800-1000 DEG C of high temperature, obtains powdery or blocks of solid；Step 2: products therefrom is placed in inertia in ball mill Ball milling 3-5h under atmosphere protection is removed irony substance in ball milling product using magnet or electromagnet；Step 3: by product and two Titanium oxide (TiO2), niobium pentaoxide (Nb2O5) after mixing under inert atmosphere protection ball milling for 24 hours, realize the titanium (Ti) to material, Niobium (Nb) doping；Step 4: by after product and sodium metasilicate (containing the crystallization water) and ammonium chloride mixing under inert atmosphere protection ball milling For 24 hours, it realizes and the silicon substrate class core-shell structure of material is constructed；Step 5: addition carbon nano-tube material and grapheme material, ball milling 12 Hour, and product is sintered in inert gas high temperature, carry out organic conductive agent cladding；Step 6: product is ground in roller Then product is sintered by pressure in inert gas high temperature, ball mill grinding rolls again, is sintered, ball mill grinding, reciprocal 2 times, most Product is obtained within ball milling 2 hours again after crushing eventually；Step 7: HF acid, which is added, performs etching removal sacrificial layer, ethyl alcohol cleaning, drying.
The beneficial effects of the present invention are: compared with prior art, the silicon-carbon cathode material prepared is stablized with high circulation The characteristics of property, high capacity, it can solve silicon-carbon cathode material bulk effect and for the first time low bottleneck problem of coulombic efficiency.
Specific embodiment
It is a kind of Silicon-carbon composite material for lithium ion battery, and structure is class core-shell structure, and class core-shell structure includes interior Core and the shell being coated on outside kernel；Kernel includes the titanium (Ti) and 5%-15% niobium of the silicon of 70%-95%, 4%-20% (Nb), silicon is the internal layer of kernel, and titanium (Ti) and niobium (Nb) element are dispersed in the surface of internal layer；Shell is by graphene and carbon nanotube It constitutes, the mass ratio with kernel is 11%-42%, and above-mentioned percentage is mass percent.
Its preparation step is as follows:
Step 1: collecting the waste silicon powder under Buddha's warrior attendant wire cutting, place it under argon gas (Ar) atmosphere in 1000 DEG C of high temperature dwells 8h is held, powdery or blocks of solid are obtained；
Step 2: step 1 products therefrom is placed in 450r/min ball milling 4h under argon gas in ball mill (Ar) atmosphere protection, Irony in ball milling product is removed using magnet；
Step 3: by titanium dioxide (TiO2), niobium pentaoxide (Nb2O5) mixed in 1 to 1 ratio, then according to 1 to 9 Ratio be added in step 2 products therefrom and mix, 450r/min ball milling is for 24 hours under argon gas (Ar) atmosphere protection；
Step 4: step 3 products therefrom and sodium metasilicate (containing the crystallization water) and ammonium chloride is mixed according to 45 to 6 ratio than 2 Ball milling is carried out for 24 hours with products therefrom under inert atmosphere protection after material, realizes and the silicon substrate class core-shell structure of material is constructed；
Step 5: adding the carbon nano-tube material and grapheme material of 0.5% mass ratio, ball milling respectively in products therefrom 12 hours, and by product in inert gas 1000 DEG C high temperature sintering 2 hours, carry out organic conductive agent cladding；
Step 6: product is rolled in roller, then product is being sintered in inert gas high temperature, ball mill grinding, It rolls, is sintered, reciprocal 2 times again, obtain final product within ball milling 2 hours again after final crushing.
Step 7: HF acid solution (10%) is added in step 6 products therefrom handles 2h, removal sacrificial layer is performed etching, Finally several times with dehydrated alcohol eccentric cleaning, drying is put into 80 DEG C of drying in vacuum oven.

Claims (4)

1. a kind of Silicon-carbon composite material for lithium ion battery, it is characterised in that the structure of Si-C composite material is class core-shell structure, Class core-shell structure includes kernel and the shell that is coated on outside kernel；Kernel includes the titanium (Ti) of the silicon of 70%-95%, 4%-20% With 5%-15% niobium (Nb), silicon is the internal layer of kernel, and titanium (Ti) and niobium (Nb) element are dispersed in the surface of internal layer；Shell is by graphite Alkene and carbon nanotube are constituted, and the mass ratio with kernel is 11%-42%, and above-mentioned percentage is mass percent.It is with Gao Xun The characteristics of ring stability, high capacity, can solve silicon-carbon cathode material bulk effect and for the first time low bottleneck problem etc. of discharging efficiency Advantage.
2. a kind of lithium ion battery silicon based composite material preparation method, it is characterised in that: carried out according to following step: step One, the waste silicon powder under Buddha's warrior attendant wire cutting is collected, places it under inert atmosphere and keeps 6-8h in 800-1000 DEG C of high temperature, obtain powder Shape or blocks of solid；Step 2: products therefrom is placed in ball mill ball milling 3-5h under inert atmosphere protection, using magnet or electricity Magnet removes irony substance in ball milling product；Step 3: by product and titanium dioxide (TiO2), niobium pentaoxide (Nb2O5) mixed Ball milling for 24 hours, realizes that the titanium (Ti) to material, niobium (Nb) adulterate under inert atmosphere protection after material；Step 4: by product and sodium metasilicate Ball milling for 24 hours, realizes the silicon substrate class core-shell structure structure to material under inert atmosphere protection after (containing the crystallization water) and ammonium chloride mixing It builds；Step 5: addition carbon nano-tube material and grapheme material, ball milling 12 hours, and product is burnt in inert gas high temperature Knot carries out organic conductive agent cladding；Step 6: product is rolled in roller, then product is burnt in inert gas high temperature Knot, ball mill grinding roll again, are sintered, ball mill grinding, reciprocal 2 times, obtain product within ball milling 2 hours again after final crushing；Step Seven, HF acid is added and performs etching removal sacrificial layer, ethyl alcohol cleaning, drying.
3. the preparation method of Silicon-carbon composite material for lithium ion battery according to claim 2, it is characterised in that described lazy Property gas be argon gas or helium.
4. the preparation method of Silicon-carbon composite material for lithium ion battery according to claim 2, it is characterised in that step 7 Drying after middle washing is vacuum drying or spray drying.
CN201810814999.1A 2018-07-18 2018-07-18 Silicon-based composite material for lithium ion battery and preparation method thereof Active CN108987717B (en)

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Cited By (5)

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CN110518226A (en) * 2019-09-10 2019-11-29 石家庄尚太科技有限公司 A kind of silicon-carbon composite cathode material and preparation method thereof
CN111081992A (en) * 2019-10-12 2020-04-28 开封大学 Preparation method of binder-free lithium ion battery negative electrode material
CN111170364A (en) * 2019-12-30 2020-05-19 北方奥钛纳米技术有限公司 Carbon-coated silicon-based titanium-niobium composite material, preparation method thereof and lithium ion battery
CN111463419A (en) * 2020-04-28 2020-07-28 苏州宇豪纳米材料有限公司 Silicon-based @ titanium niobium oxide core-shell structure anode material and preparation method thereof
CN112234189A (en) * 2020-10-13 2021-01-15 深圳大学 Tin telluride-based electrode material, preparation method thereof and lithium ion battery

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110518226A (en) * 2019-09-10 2019-11-29 石家庄尚太科技有限公司 A kind of silicon-carbon composite cathode material and preparation method thereof
CN110518226B (en) * 2019-09-10 2020-10-27 石家庄尚太科技有限公司 Silicon-carbon composite negative electrode material and preparation method thereof
CN111081992A (en) * 2019-10-12 2020-04-28 开封大学 Preparation method of binder-free lithium ion battery negative electrode material
CN111081992B (en) * 2019-10-12 2021-10-12 开封大学 Preparation method of binder-free lithium ion battery negative electrode material
CN111170364A (en) * 2019-12-30 2020-05-19 北方奥钛纳米技术有限公司 Carbon-coated silicon-based titanium-niobium composite material, preparation method thereof and lithium ion battery
CN111463419A (en) * 2020-04-28 2020-07-28 苏州宇豪纳米材料有限公司 Silicon-based @ titanium niobium oxide core-shell structure anode material and preparation method thereof
CN111463419B (en) * 2020-04-28 2022-04-01 苏州宇豪纳米材料有限公司 Silicon-based @ titanium niobium oxide core-shell structure anode material and preparation method thereof
CN112234189A (en) * 2020-10-13 2021-01-15 深圳大学 Tin telluride-based electrode material, preparation method thereof and lithium ion battery

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