CN102623683A - A method of using industrial silicon powder as negative electrode material of lithium ion battery - Google Patents
A method of using industrial silicon powder as negative electrode material of lithium ion battery Download PDFInfo
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- CN102623683A CN102623683A CN2012101066543A CN201210106654A CN102623683A CN 102623683 A CN102623683 A CN 102623683A CN 2012101066543 A CN2012101066543 A CN 2012101066543A CN 201210106654 A CN201210106654 A CN 201210106654A CN 102623683 A CN102623683 A CN 102623683A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
Disclosed is a process for using industrial silicon powder as cathode materials of lithium ion batteries, which comprises the steps of 1) adding deionized water to the industrial silicon powder, conductive black, an binding agent and a dispersing agent, and mixing the mixture; 2) evenly stirring and mixing with a magnetic stirring rod, and obtaining a paste; and 3) evenly spreading the paste on a surface of a current collector, and obtaining an electrode plate after drying. The process has the advantages that the price is low because the price of the industrial silicon powder is far below high purity silicon; alloying elements which are contained in the industrial silicon power can not only improve the electrical conductivity but also relieve the volume effect during lithium deintercalation of silicon, and a process of pure silicon doping is omitted; and the demand pressure for the high purity silicon is reduced, environmental pollution caused by silicon purification is relieved, and the process is energy-saving and environment friendly.
Description
[technical field]
The present invention relates to lithium ion battery negative material, particularly a kind of with the method for industrial silica fume as lithium ion battery negative material.
[background technology]
Along with the exploitation of dynamic lithium battery, the high power capacity negative material is absolutely necessary.Silicon (Si) has the theoretical embedding lithium capacity near 4200mAh/g, has become one of main negative material of present research at present.But the cycle performance of silicon is relatively poor, and this is two shortcomings because of the silicon-based anode material, and one is with bigger change in volume in charge and discharge process; Producing the silicon grain breaks and powder phenomenon-tion; Cause separating between conductive network and the silicon particle, internal resistance increases suddenly, and capacity descends fast; HIGH-PURITY SILICON is nonconducting on the other hand, afterwards could be as electrode material so need mix perhaps modification to HIGH-PURITY SILICON.
To two shortcomings of above pure silicon, the following method of main at present employing is that pure silicon is carried out modification: 1) silicon materials nanometerization.Make the electrode material of acquisition have abundant space to alleviate the bulk effect of silicon.The refinement of particle has increased the specific area of silicon, makes lithium atom embed more easily and deviates from; The nano silicone material can be alleviated bulk effect, improves cycle performance.But nano material is reunited easily, can not fundamentally solve the cyclical stability problem.2) silicon materials coat.Mainly be to utilize material with carbon element to coat now, coat on the one hand and can improve conductivity that on the other hand, carbon class material can be alleviated the efflorescence refinement that the silicon grain volumetric expansion causes on the surface of silicon grain, makes cycle performance better; Silicon bag carbon Si/C composite material can have higher capacity and cycle performance than material with carbon element; But the content of silicon has very big influence to the performance of material; When silicone content was higher, silicon grain had had bulk effect in the process of removal lithium embedded on the one hand, and it is unstable that structure becomes; And in follow-up circulation, cover the surface silicon show tangible bulk effect, make the cyclical stability of material sharply descend.The composite material that contains minor amount of silicon also fails to suppress the reduction of capacity in cyclic process; Maybe be because a little less than the silicon and graphite adhesion of surface exposure; Si separates with graphite and reunites in cyclic process, so silicon carbon coated composite material can not improve capacity and cyclical stability simultaneously.3) doping of silicon materials.Mainly be to utilize the mechanical alloying method to mix alloying elements to silica flour at present, main purpose is to improve conductivity, and alloying element can improve silicon crystalline structure, alleviates bulk effect effectively.
At present the modification of silicon is carried out on high-purity silicon powder basically, more than 99.9999% (6N), material cost is high usually for the high-purity silicon powder silicone content.The HIGH-PURITY SILICON material is meant by single silicon atom to be formed, and silicon atom is regularly arranged polysilicon at three dimensions.When utilizing HIGH-PURITY SILICON to make electrode material, need carry out modification and improve the conductivity of electrode material itself with mixing to it.Since in follow-up making electrode need to high-purity silicon powder mix with modification improving its conductivity, reduce the volumetric expansion in the storage lithium process, need be raw material with the HIGH-PURITY SILICON not necessarily during as electrode material so silicon.
Industrial silica fume is claimed metallic silicon power again, is silver gray or lead powder, and metallic luster is arranged; Its fusing point is high, heat resistance is good, resistivity is high; Having the heigh antioxidation effect, be called as " industrial monosodium glutamate ", is the indispensable basic raw materials of a lot of high-tech industries.In the industry, normally in electric furnace, make metallic silicon by carbon reduction silicon dioxide.Chemical equation is: SiO2+2C → Si+2CO.The silicon purity that makes like this is 97-98%, and all the other compositions are iron, aluminium, and calcium etc. also are metallic silicon, and particle diameter is between 1um-100um, and metallic silicon divides a lot of kinds, is with silicon, iron, aluminium, the content of calcium is classified.
Industrial silica fume is mainly used in the following aspects at present:
1) industrial silica fume is widely used in refractory material, the powder metallurgy industry, improving the high temperature resistant of product, and wear-resistant and non-oxidizability, its product is widely used in converter, kiln, the kiln furnitures;
2) in the organic silicon chemical industry, industrial silica fume is the synthetic basic material of organosilicon macromolecule, as is used to produce silicon monomer, silicone oil, silicon rubber anticorrisive agent, thus characteristics such as the heat-resisting quantity of raising product, electrical insulating property, corrosion resistance, anticorrosive property, waterproof;
3) industrial silica fume is made by the pull into monocrystalline silicon, and the silicon chip that processes is widely used in high-tech area, is integrated circuit, the requisite raw material of electronic component;
4) in the metallurgical casting industry, industrial silica fume is as non-ferrous alloy additive, si fe alloy agent, thus the raising steel hardenability.Industrial silica fume also can be applicable to the reducing agent of some metal, is used for new ceramics alloy etc.
Utilize industrial silica fume not appear in the newspapers at present as the domestic of lithium ion battery negative material.
[summary of the invention]
The objective of the invention is to above-mentioned technical Analysis; Provide a kind of with the method for industrial silica fume as lithium ion battery negative material; Have high power capacity, excellent performance, cheap advantage as the industrial silica fume of lithium ion battery negative material; Can expand the scope of application of industrial silica fume, satisfy the needs of people high power capacity small size battery.
Technical scheme of the present invention:
A kind of with the method for industrial silica fume as lithium ion battery negative material, step is following:
1) industrial silica fume, conductive black, binding agent and dispersant being added deionized water mixes;
2) utilize magnetic stirring bar to mix, make pastel;
3) pastel is uniformly coated on collection liquid surface, promptly makes electrode slice after the oven dry.
The particle diameter of said industrial silica fume is 10-100um; The specific area of conductive black is 10-3000m
2/ g; Binding agent is butadiene-styrene rubber (SBR); Dispersant is CMC (CMC).
The mass ratio of said silicon materials, conductive black, binding agent (SBR), dispersant (CMC) is 85: 10: 2: 3.
Said solid material is modulated into slurry with deionized water, and the mass ratio of solid material and deionized water is 1: 0.5-2.
Said collector is Copper Foil or nickel foam, and pastel is 2-10mg/cm with the quality surface ratio of collector
2
Advantage of the present invention:
1) price of industrial silica fume is well below HIGH-PURITY SILICON, and is cheap;
2) alloying element in the industrial silica fume both can improve conductivity, can alleviate the bulk effect of silicon when removal lithium embedded again, had avoided the operation that pure silicon is mixed;
3) alleviated China to the HIGH-PURITY SILICON demand pressure, the environmental pollution that produces when alleviating silicon and purifying, not only environmental protection but also energy-conservation.
[embodiment]
Below tell about detailed process of the present invention through embodiment, it is the convenience in order to understand that embodiment is provided, never be the restriction the present invention.
Embodiment:
A kind of with the method for industrial silica fume as lithium ion battery negative material, step is following:
1) be that industrial silica fume, the 10g specific area of 10um is 250m with the 85g particle diameter
2The conductive black of/g, 2g binding agent butadiene-styrene rubber (SBR) and 3g dispersant CMC (CMC) add the 100g deionized water and mix;
2) utilize magnetic stirring bar to mix, make pastel;
3) pastel is uniformly coated on copper foil surface, pastel is 3mg/cm with the quality surface ratio of Copper Foil
2, promptly make electrode slice after the oven dry.
Detect and show: the initial charge capacity of metallic silicon is 1500mAh/g, and the specific capacity of loss 46% improves more than 80% than pure silicon.Charge/discharge capacity is kept to 170mAh/g after ten circulations of pure silicon, and charge/discharge capacity is about 800mAh/g after 10 circulations of metallic silicon.More than experiment shows that the cycle performance of metallic silicon will be greatly improved than pure silicon.
Claims (5)
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| CN2012101066543A CN102623683A (en) | 2012-04-12 | 2012-04-12 | A method of using industrial silicon powder as negative electrode material of lithium ion battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103779536A (en) * | 2013-11-06 | 2014-05-07 | 南京安普瑞斯有限公司 | Silicon-containing negative electrode of lithium ion battery and preparation method of silicon-containing negative electrode |
| CN103887476A (en) * | 2014-04-09 | 2014-06-25 | 天津理工大学 | Method for preparing lithium ion battery anode material from industrial silicon powder |
Citations (2)
| 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 |
| CN1933214A (en) * | 2005-09-13 | 2007-03-21 | 三星Sdi株式会社 | Anode and lithium battery including the anode |
-
2012
- 2012-04-12 CN CN2012101066543A patent/CN102623683A/en active Pending
Patent Citations (2)
| 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 |
| CN1933214A (en) * | 2005-09-13 | 2007-03-21 | 三星Sdi株式会社 | Anode and lithium battery including the anode |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103779536A (en) * | 2013-11-06 | 2014-05-07 | 南京安普瑞斯有限公司 | Silicon-containing negative electrode of lithium ion battery and preparation method of silicon-containing negative electrode |
| CN103779536B (en) * | 2013-11-06 | 2017-01-04 | 南京安普瑞斯有限公司 | Silicon-containing cathode of lithium ion battery and preparation method thereof |
| CN103887476A (en) * | 2014-04-09 | 2014-06-25 | 天津理工大学 | Method for preparing lithium ion battery anode material from industrial silicon powder |
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Application publication date: 20120801 |