CN103887476A - Method for preparing lithium ion battery anode material from industrial silicon powder - Google Patents

Method for preparing lithium ion battery anode material from industrial silicon powder Download PDF

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Publication number
CN103887476A
CN103887476A CN201410139871.1A CN201410139871A CN103887476A CN 103887476 A CN103887476 A CN 103887476A CN 201410139871 A CN201410139871 A CN 201410139871A CN 103887476 A CN103887476 A CN 103887476A
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China
Prior art keywords
silicon
industrial
silica fume
ion battery
lithium ion
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Pending
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CN201410139871.1A
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Chinese (zh)
Inventor
姜训勇
昂亚峰
任芯仪
窦振博
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Tianjin University of Technology
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Tianjin University of Technology
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Priority to CN201410139871.1A priority Critical patent/CN103887476A/en
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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
    • H01M4/13—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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • 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
    • 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 method for preparing a lithium ion battery anode material from industrial silicon powder. The method comprises the following steps of (1) grinding industrial silicon alloy to prepare industrial silicon powder; (2) sufficiently mixing industrial silicon powder with a conductive agent, an adhesive, a dispersant and a solvent, wherein the mass ratio of industrial silicon powder to conductive agent to adhesive to dispersant is (70-90):(2-15):(1-3); (3) uniformly coating electrode paste on the surface of a current collector, and drying to obtain an ion battery electrode plate. The method has the advantages that (1) industrial silicon alloy used in the method is far cheaper than high-purity silicon so as to be low in price; (2) alloy elements in industrial silicon alloy not only can be used for improving the conductivity, but also can be used for relieving the volume effect of silicon during lithiation and omitting the process for doping pure silicon; (3) the demand pressure for high-purity silicon in China is relieved, the environment pollution caused by silicon purification is reduced, the environment is protected, and the energy is saved.

Description

A kind of by industrial silica fume the method for the preparation of lithium ion battery negative material
Technical field
The present invention relates to the preparation of lithium ion battery negative material, particularly a kind of by industrial silica fume the method for the preparation of lithium ion battery negative material.
Background technology
Along with the exploitation of dynamic lithium battery, high power capacity negative material is absolutely necessary.Silicon (Si) has the theoretical embedding lithium capacity that approaches 4200mAh/g, has now become one of main negative material of current research.But the cycle performance of silicon is poor, this is two shortcomings because of silicon based anode material, and one is with larger change in volume in charge and discharge process, producing silicon grain breaks and powder phenomenon-tion, cause separating between conductive network and silicon particle, internal resistance increases suddenly, capacity fast-descending; HIGH-PURITY SILICON is nonconducting on the other hand, thus need to HIGH-PURITY SILICON adulterate or modification after could serve as electrode material.
For two shortcomings of above pure silicon, usually adopting following methods is that pure silicon is carried out to modification: 1) silicon materials nanometer, makes the electrode material obtaining have abundant space to alleviate the bulk effect of silicon.The refinement of particle has increased the specific area of silicon, makes lithium atom more easily embed and deviate from; Nano silicone material can be alleviated bulk effect, improves cycle performance.But nano material is easily reunited, can not fundamentally solve cyclical stability problem.2) silicon materials are coated, are mainly to utilize material with carbon element to be coated, and are coated and can improve conductivity on the one hand, and on the other hand, carbon class material, on the surface of silicon grain, can be alleviated the efflorescence refinement that silicon grain volumetric expansion causes, and makes cycle performance better.Silicon bag carbon Si/C composite material can have higher capacity and cycle performance compared with material with carbon element, but the content of silicon has a great impact the performance of material, the one, in the time that silicone content is higher, silicon grain has had bulk effect in the process of removal lithium embedded, and it is unstable that structure becomes; In follow-up circulation, cover in addition surperficial silicon and show obvious bulk effect, the cyclical stability of material is sharply declined.In cyclic process, also fail to suppress the reduction of capacity containing the composite material of a small amount of silicon, this is because a little less than the silicon and graphite adhesion of surface exposure, in cyclic process, Si separates with graphite and reunites, so silicon carbon coated composite material can not improve capacity and cyclical stability simultaneously.3) doping of silicon materials, is mainly to utilize Mechanical Alloying to mix alloying elements to silica flour at present, and object is to improve conductivity, and alloying element can improve silicon crystalline structure, effectively alleviates bulk effect.
At present the modification of silicon is carried out substantially in high-purity silicon powder, high-purity silicon powder silicone content is conventionally more than 99.9999%.The conductivity of HIGH-PURITY SILICON itself is poor, in the time utilizing HIGH-PURITY SILICON to make electrode material, need to carry out modification and adulterate and improve the conductivity of electrode material itself it.Since need high-purity silicon powder to carry out doping and modification to improve its conductivity in follow-up making electrode, to reduce the volumetric expansion in storage lithium process, not necessarily need to be taking HIGH-PURITY SILICON as raw material during so using silicon as electrode material.Based on this point, the present invention proposes to adopt the industrial silica fume that contains certain alloy atom as lithium ion battery negative pole active materials.
Industrial silica fume claims again metallic silicon power, is silver gray or lead powder, has metallic luster, its fusing point is high, heat resistance good, resistivity is high, having heigh antioxidation effect, be called as " industrial monosodium glutamate ", is the indispensable basic raw materials of a lot of high-tech industries.Industrial, normally in electric furnace, make metallic silicon by carbon reduction silicon dioxide.Chemical equation is: SiO2+2C → Si+2CO.The silicon alloy making is like this industrial silicon, is also metallic silicon.In industrial silica fume, principal component is silicon, and wherein contained alloying element is one or more the combination such as iron, aluminium, calcium.Total alloying element content is at 0.001-3%(mass ratio) between.The particle diameter of industrial silica fume is between 1um-100um.
Industrial silica fume is mainly used in the following aspects at present:
1), for refractory material, Powder Metallurgy Industry, to improve high temperature resistant, the wear-resistant and non-oxidizability of product, its product is widely used in converter, kiln, kiln furnitures;
2) in organic silicon chemical industry, industrial silica fume is the synthetic basic material of organosilicon macromolecule, as for the production of silicon monomer, silicone oil, silicon rubber anticorrisive agent, thereby improve the characteristic such as heat-resisting quantity, electrical insulating property, corrosion resistance, anticorrosive property, waterproof of product;
3) industrial silica fume is made by the pull into the silicon chip that monocrystalline silicon processes and is widely used in high-tech area, is integrated circuit, the requisite raw material of electronic component;
4), in metallurgical casting industry, industrial silica fume is as non-ferrous alloy additive, si fe alloy agent, thus raising steel hardenability.Industrial silica fume also can be applicable to the reducing agent of some metal, for new ceramics alloy etc.
Utilize at present domestic the have no report of industrial silica fume as lithium ion battery negative material.
Summary of the invention
The object of the invention is for above-mentioned technical Analysis and existing problems, provide a kind of by industrial silica fume the method for the preparation of lithium ion battery negative material, the method industrial use silicon alloy used has advantages of high power capacity, excellent performance, cheap, can expand the scope of application of industrial use silicon alloy, meet the needs of people to high power capacity small size battery.
Technical scheme of the present invention:
A method by industrial silica fume for the preparation of lithium ion battery negative material, step is as follows:
1) industrial silicon alloy is adopted mechanical ball milling or airflow milling method grind, make the industrial silica fume that particle diameter is not more than 60um;
2) above-mentioned industrial silica fume is fully mixed with conductive agent, binding agent, dispersant and solvent, make electrode slurry;
3) electrode slurry is evenly coated in to collection liquid surface, after oven dry, can makes ion battery electrode slice.
In described industrial silicon alloy, contained alloying element is the combination of one or more arbitrary proportions in iron, aluminium and calcium, and the mass percent of alloying element total content is 0.001-3%.
The particle diameter of described industrial silica fume is not more than 60um, and conductive agent is that specific area is 10-3000m 2the conductive black of/g, binding agent is butadiene-styrene rubber (SBR), and dispersant is CMC (CMC), and solvent is deionized water; The mass ratio of industrial silica fume and conductive agent, binding agent, dispersant and solvent is 70-90:2-15:1-3.
Described collector is Copper Foil or nickel foam, and electrode slurry is 1-10mg/cm at the coated weight of collection liquid surface 2.
Advantage of the present invention is:
1) price of the method industrial silicon alloy used is well below HIGH-PURITY SILICON, cheap;
2) alloying element in industrial silicon alloy both can improve conductivity, can alleviate again the bulk effect of silicon in the time of removal lithium embedded, had avoided the operation that pure silicon is adulterated;
3) alleviate China to HIGH-PURITY SILICON demand pressure, alleviated the environmental pollution producing when silicon is purified, not only environmental protection but also energy-conservation.
[brief description of the drawings]
Accompanying drawing is industrial silica fume and pure silicon powder charge-discharge performance correlation curve.
[embodiment]
Tell about by the following examples detailed process of the present invention, it is the convenience in order to understand that embodiment is provided, and is never restriction the present invention.
Embodiment:
A method by industrial silica fume for the preparation of lithium ion battery negative material, step is as follows:
1) adopt mechanical ball-milling method to grind industrial silicon alloy, make the industrial silica fume that particle diameter is 10um;
2) be 250m by above-mentioned 85g industrial silica fume and 10g specific area 2conductive black conductive agent, 2g benzene rubber (SBR) binding agent, 3g CMC (CMC) dispersant and the 100g deionized water of/g are uniformly mixed with magnetic stirring bar, make electrode slurry;
3) above-mentioned electrode slurry is evenly coated in to copper foil of affluxion body surface, electrode slurry is 3mg/cm at the coated weight of collection liquid surface 2, after oven dry, can make ion battery electrode slice.
Accompanying drawing is industrial silica fume and pure silicon powder charge-discharge performance correlation curve, shows: the initial charge capacity of industrial silica fume is 1500 mAh/g in figure, and the specific capacity of loss 46%, improves more than 80% than pure silicon powder.After ten circulations of pure silicon powder, charge/discharge capacity is kept to 170 mAh/g, and after 10 circulations of industrial silica fume, charge/discharge capacity is 800 mAh/g left and right.More than experiment shows that the cycle performance of industrial silica fume silicon is greatly improved than pure silicon powder.

Claims (4)

1. the method for the preparation of lithium ion battery negative material by industrial silica fume, is characterized in that step is as follows:
1) industrial silicon alloy is adopted mechanical ball milling or airflow milling method grind, make industrial silica fume;
2) above-mentioned industrial silica fume is fully mixed with conductive agent, binding agent, dispersant and solvent, make electrode slurry;
3) electrode slurry is evenly coated in to collection liquid surface, after oven dry, can makes ion battery electrode slice.
2. the method for the preparation of lithium ion battery negative material by industrial silica fume according to claim 1, it is characterized in that: in described industrial silicon alloy, contained alloying element is the combination of one or more arbitrary proportions in iron, aluminium and calcium, the mass percent of alloying element total content is 0.001-3%.
3. the method for the preparation of lithium ion battery negative material by industrial silica fume according to claim 1, is characterized in that: the particle diameter of described industrial silica fume is not more than 60um, conductive agent is that specific area is 10-3000m 2the conductive black of/g, binding agent is butadiene-styrene rubber, and dispersant is CMC, and solvent is deionized water; The mass ratio of industrial silica fume and conductive agent, binding agent, dispersant is 70-90:2-15:1-3.
4. the method for the preparation of lithium ion battery negative material by industrial silica fume according to claim 1, is characterized in that: described collector is Copper Foil or nickel foam, electrode slurry is 1-10mg/cm at the coated weight of collection liquid surface 2.
CN201410139871.1A 2014-04-09 2014-04-09 Method for preparing lithium ion battery anode material from industrial silicon powder Pending CN103887476A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1744356A (en) * 2004-09-03 2006-03-08 信越化学工业株式会社 Non-aqueous electrolyte secondary cell negative electrode material and metallic silicon power therefor
CN102623683A (en) * 2012-04-12 2012-08-01 天津理工大学 Process for using industrial silicon powder as cathode materials of lithium ion batteries

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1744356A (en) * 2004-09-03 2006-03-08 信越化学工业株式会社 Non-aqueous electrolyte secondary cell negative electrode material and metallic silicon power therefor
CN102623683A (en) * 2012-04-12 2012-08-01 天津理工大学 Process for using industrial silicon powder as cathode materials of lithium ion batteries

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Application publication date: 20140625