CN103633305B - Lithium ion battery silicon composite cathode material and preparation method thereof - Google Patents

Lithium ion battery silicon composite cathode material and preparation method thereof Download PDF

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CN103633305B
CN103633305B CN201310669739.7A CN201310669739A CN103633305B CN 103633305 B CN103633305 B CN 103633305B CN 201310669739 A CN201310669739 A CN 201310669739A CN 103633305 B CN103633305 B CN 103633305B
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silicon
metal
preparation
compound
composite
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CN103633305A (en
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包志豪
李晓冬
姚莉
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SUZHOU YUHAO NANO MATERIALS Co Ltd
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SUZHOU YUHAO NANO MATERIALS Co Ltd
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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
    • 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
    • H01M4/626—Metals
    • 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
    • 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 kind of lithium ion battery silicon composite and preparation method thereof.Preparation method comprises the predecessor utilizing multiporous biological silica substrate metal oxide-impregnated, after drying, at high temperature resolve into the compound of silicon dioxide and metal or nonmetal oxide, then magnesium thermit is utilized, oxygen reduction SiClx becomes silicon and metal with metal oxide simultaneously, again by chlorohydric acid pickling, obtain silicon and metal or nonmetallic compound.In this composite material, metal is evenly distributed in the hole of porous silicon, be conducive to the conductance improving silicon, when this material is as lithium ion battery negative material, metal wherein or nonmetal as inert material, plays connection and supporting role to silicon materials, contribute to the swelling stress that alleviation volume brings, therefore there is reversible capacity high, good cycle, the advantage of high rate performance excellence.

Description

Lithium ion battery silicon composite cathode material and preparation method thereof
Technical field
The present invention relates to a kind of lithium ion battery silicon composite cathode material and preparation method thereof.
Background technology
At present, the negative material of business-like lithium ion battery mainly uses graphite material, but the theoretical capacity of graphite material (372 mAh/g), the demand of height ratio capacity lithium ion cannot be met, silicon has theoretical capacity high in current negative material, it is a kind of negative material of novel lithium ion battery, but silicon has larger change in volume in the process of discharge and recharge, produce larger effect of stress, make positive pole differentiation degree serious, the intrinsic conductivity of silicon is lower in addition, is unfavorable for carrying out high power charging-discharging.Study the Material cladding by carbon and silicon in the past, solve the application problem of above-mentioned silicium cathode material.Patent CN1909266A discloses a kind of method of a kind of copper silicon carbon composite prepared by high-energy ball milling, the composite material aperture obtained is at 1-50nm, copper content is about 20 wt%, carbon content is about 30 wt%, this material has good charge and discharge cycles stability, but reversible capacity is lower, be about about 580 mAh/g.And copper can not obtain with silicon and mixes very uniformly.Advanced Materials magazine has reported a kind of macropore silicon composite in 2010 in 12 phase 1-4.First prepare the elemental silicon with three-dimensional structure with magnesiothermic reduction reaction, again by silver mirror reaction depositing silver nano particle in macropore silicon, macropore silicon is mono-crystalline structures, and its grain diameter is 1-5 micron, aperture is at 200 ran, and 100 circulations remain on 2200 mAh/g.Although silver-silicon compound improves reversible capacity and the high rate performance of material, the use of silver increases considerably the production cost of material, is unfavorable for its commercial applications.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, discloses a kind of preparation method of lithium ion battery silicon composite cathode material.The present invention, by magnesium thermit, reduces after silicon dioxide and metal oxide simultaneously, obtains the compound of porous silicon and metal, for lithium ion battery negative material.
Saying of general introduction, the present invention utilizes the predecessor of multiporous biological silica substrate metal oxide-impregnated, after drying, at high temperature resolve into silicon dioxide and metal composite, then magnesium thermit is utilized, oxygen reduction SiClx becomes silicon and metal with metal oxide simultaneously, then by chlorohydric acid pickling, obtains the compound of silicon and metal.
The present invention needs the technical scheme protected to be characterized by:
A preparation method for lithium ion battery silicon composite cathode material, is characterized in that, be the preparation method of silicon and metal composite, method step is followed successively by:
Step 1: will mesoporous silicon oxide predecessorimpregnated in 0.01 M--12 M(mol/L) the precursor solution of metal oxidein, after its abundant absorbent solution, filter, dry, obtain mixture.
Step 2: the mixture that step 1) obtains is heated to 300-850 degree Celsius in atmosphere, burns 2-6 hour, obtains the compound of porous silica and metal oxide.
Step 3: by step 2) compound and the magnesium powder that obtain be after 1:0.1--20 mixes in mass ratio, and be heated to 600-850 degree Celsius in an inert atmosphere, keep 2-12 hour.
Step 4: by step 3) obtain product cooling after, immerse 0.2-6M(mol/L) aqueous hydrochloric acid solution, removing impurity, after filtration, cleaning and drying after obtain porous silicon and metallic composite.
Described metallic element can be draw together copper, titanium or nickel, or their mixed form.
In step 1, described mesoporous silicon oxide predecessor, this raw material can select rice hull ash, diatomite or bagasse ash, or it mixes arbitrarily.
In step 1, the predecessor of described metal oxide is titanium, the nitrate of copper and mickel, chlorate or acetate, and metatitanic acid four fourth fat.The precursor solution of described metal oxide, this solution can be its aqueous solution or ethanolic solution.
In step 3, described inert gas can select argon gas, nitrogen or hydrogen argon, or its mist.
Finally, the present invention prepares end-product silicon/metallic composite, its structure composition is characterized by: be made up of porous silicon matrix and the metal be distributed in porous silicon pores, wherein metal and nonmetal silicon consist of 1-70 wt%, porous silicon matrix is polycrystalline structure, its grain diameter is at 5 nm-100 μm, and aperture is at 0.001-5 μm, and hole is at 0.1-2.0 cm 3/ g, specific area is at 5-300 m 2/ g.
In the composite material that the inventive method prepares, metal is evenly distributed in the hole of porous silicon, be conducive to the conductance improving silicon, when this material is as lithium ion battery negative material, metal wherein, as inert material, plays connection and supporting role to silicon materials, contribute to the swelling stress that alleviation volume brings, therefore there is reversible capacity high, good cycle, the advantage of high rate performance excellence.
Therefore, compared with prior art, technical solution of the present invention beneficial effect is:
1. abundant raw material source, cheap, technique is simple.
2. in the duct in natural porous bio-silicon dioxide, immerse metal oxide is reduced into porous silicon and metal compound through magnesium thermit one step.
3. the porous silicon and after metal composite, because electric conductivity and mechanical performance improve, when it is as ion cathode material lithium, capacity and preservation characteristics all obtain large increase.
Accompanying drawing explanation
Fig. 1. the electron microscope image of copper/silicon compound that the present invention obtains by embodiment 1.
Fig. 2. the elementary analysis of copper/silicon compound that the present invention obtains by embodiment 1.
Fig. 3. the present invention by embodiment 1 obtain copper/silicon compound with not with the contrast of the silicon cycling preservation characteristics of copper compound.
Fig. 4. copper/silicon compound that the present invention obtains by embodiment 1 with not with the contrast as electrochemical impedance spectroscopy during lithium ion cell electrode of the silicon of copper compound.
Embodiment
Below by way of specific embodiment and accompanying drawing, technical solution of the present invention is described further, verifies.
embodiment 1
1) be 4M(mol/L by immersing concentration after diatomite grinding) copper nitrate the aqueous solution in, after its abundant absorbent solution, to filter, dry.
2) mixture step 1) obtained is under 600 degrees Celsius, and calcination 2 hours, obtains oxide and diatomaceous compound.
3) by step 2) compound that obtains mixes according to mass ratio 1:1 with metal magnesium powder, is heated to 650 degrees Celsius under an argon atmosphere, is incubated 7 hours,
4) be soak filtration after 12 hours, cleaning and drying in the aqueous hydrochloric acid solution of 2M, the compound of acquisition copper/porous silicon in concentration by solid mixture after naturally cooling.As shown in Figure 1 and Figure 2, copper/the porous silicon composite material of final acquisition, its structure composition is characterized by: be made up of porous silicon matrix and the metal be distributed in porous silicon pores, wherein metal and nonmetallicly consist of 1-70 wt%, porous silicon matrix is polycrystalline structure, its grain diameter is at 5 nm-100 μm, and aperture is at 0.001-5 μm, and hole is at 0.1-2.0 cm 3/ g, specific area is at 5-300 m 2/ g.
The aqueous solution of copper/porous silicon composite material step 4) finally obtained and conductive agent (trade name: Super P) and sodium alginate is according to 6:2:2(mass ratio) ratio mixed preparing uniformly slurry, by slurry coating on Copper Foil collection collector, cathode pole piece is pressed into after 120 degrees Celsius of vacuumize, being to electrode with metal lithium sheet, take concentration as the LiPF of 1M 6ethylene carbonate, dimethyl carbonate and carbonic acid diethyl ester (1:1:1 v/v) solution be electrolyte, Celgard 2400 is barrier film, is assembled into button cell under a dry, inert, discharge and recharge by voltage be 5 mV-1.0 V.In the discharge and recharge of 1A/g than under electric current, reversible capacity remain on 890 mAh/g. and not with the porous silicon of copper compound, its specific capacity will be far smaller than this numerical value.As shown in Figure 4, also show the impedance analysis of electrode, the electrode be made up of copper/porous silicon composite material, its interfacial migration resistance is less than the electrode do not formed with the porous silicon of copper compound.
embodiment 2
1) will rice hull ashimmersing concentration after grinding is 0.01M(mol/L) metatitanic acid four fourth fat ethanolic solution in, after its abundant absorbent solution, to filter, dry.
2) by step 1) obtain mixture at 300 degrees Celsius, calcination 6 hours, obtain oxide with rice hull ashcompound.
3) by step 2) compound that obtains mixes according to mass ratio 1:2 with metal magnesium powder, is heated to 600 degrees Celsius under an argon atmosphere, is incubated 8 hours,
4) be soak filtration after 12 hours, cleaning and drying in the aqueous hydrochloric acid solution of 0.5M, the compound of acquisition copper/porous silicon in concentration by solid mixture after naturally cooling.
embodiment 3
1) will bagasse ashimmersing concentration after grinding is 12M(mol/L) nickel acetate the aqueous solution in, after its abundant absorbent solution, to filter, dry.
2) by step 1) obtain mixture under 850 degrees Celsius, calcination 2 hours, obtain oxide with bagasse ashcompound.
3) by step 2) compound that obtains mixes according to mass ratio 1:20 with metal magnesium powder, is heated to 850 degrees Celsius under an argon atmosphere, is incubated 2 hours,
4) be soak filtration after 12 hours, cleaning and drying in the aqueous hydrochloric acid solution of 6M, the compound of acquisition copper/porous silicon in concentration by solid mixture after naturally cooling.

Claims (2)

1. a preparation method for lithium ion battery silicon composite cathode material, is characterized in that, be the preparation method of silicon and metal composite, method step is followed successively by:
Step 1: be impregnated in by mesoporous silicon oxide predecessor in the precursor solution of 0.01M--12M metal oxide, after its abundant absorbent solution, filters, dries, obtain mixture;
Step 2: mixture step 1 obtained is heated to 300-850 degree Celsius in atmosphere, calcination 2-6 hour, obtains the compound of porous silica and metal oxide;
Step 3: compound step 2 obtained and magnesium powder after 1:0.1--20 mixes in mass ratio, are heated to 600-850 degree Celsius in an inert atmosphere, keeps 2-12 hour;
Step 4: after product cooling step 3 obtained, immerse the aqueous hydrochloric acid solution of 0.2-6M, removing impurity, after filtration, cleans and obtains porous silicon and metallic composite after drying;
In step 1, described mesoporous silicon oxide predecessor, its raw material is selected from rice hull ash, diatomite or bagasse ash, or it mixes arbitrarily;
In step 1, the predecessor of described metal oxide is titanium, the nitrate of copper and mickel, chlorate or acetate, or is metatitanic acid four fourth fat.
2. silicon/the metallic composite prepared by preparation method according to claim 1, it is characterized in that, be made up of porous silicon matrix and the metal be distributed in porous silicon pores, wherein metal and nonmetal silicon consist of the 1-70wt% accounting for whole composite material, porous silicon matrix is polycrystalline structure, its grain diameter is at 5nm-100 μm, and aperture is at 0.001-5 μm, and hole is at 0.1-2.0cm 3/ g, specific area is at 5-300m 2/ g.
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CN104157826B (en) * 2014-08-07 2016-06-08 国家电网公司 The preparation method of a kind of nano-electrode negative material
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CN105261792B (en) * 2015-07-21 2018-04-06 苏州迪思伏新能源科技有限公司 The manufacture method of the high-energy-density secondary lithium battery of Si negative poles and rich lithium richness manganese positive pole
CN105336934B (en) * 2015-11-21 2017-10-20 中国计量学院 A kind of preparation method of silicon electrode composite
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CN106602022A (en) * 2016-12-24 2017-04-26 东北电力大学 Method for preparing porous silicon/TiO2 composite negative electrode material by taking diatomite as raw material
CN107195871A (en) * 2017-04-06 2017-09-22 中国计量大学 A kind of preparation method that SiOx/C negative materials are synthesized by carrier low temperature of carbon material
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
CN110697718A (en) 2019-06-18 2020-01-17 宁德新能源科技有限公司 Porous material, preparation method thereof, negative electrode containing porous material and device
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CN113224279B (en) * 2021-07-07 2021-09-10 北京壹金新能源科技有限公司 Silica-based composite negative electrode material capable of improving first coulombic efficiency and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080086121A (en) * 2007-03-21 2008-09-25 주식회사 소디프신소재 Negative active material for a lithium secondary battery, method of preparing thereof, and lithium secondary battery comprising the same
EP2184798A1 (en) * 2008-11-10 2010-05-12 Samsung Electronics Co., Ltd. Anode active material, anode comprising the anode active material, lithium battery comprising the anode, and method of preparing the anode active material.
CN102569726A (en) * 2010-12-30 2012-07-11 中国电子科技集团公司第十八研究所 Method for preparing lithium ion battery anode material coated with metal ions
CN102983313A (en) * 2012-12-05 2013-03-20 奇瑞汽车股份有限公司 Silicon-carbon composite material and preparation method thereof, and lithium ion battery
CN103346300A (en) * 2013-06-08 2013-10-09 合肥国轩高科动力能源股份公司 Method for in-situ synthesizing silicate/carbon composite cathode material by taking rice husk carbon as silicon source

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080086121A (en) * 2007-03-21 2008-09-25 주식회사 소디프신소재 Negative active material for a lithium secondary battery, method of preparing thereof, and lithium secondary battery comprising the same
EP2184798A1 (en) * 2008-11-10 2010-05-12 Samsung Electronics Co., Ltd. Anode active material, anode comprising the anode active material, lithium battery comprising the anode, and method of preparing the anode active material.
CN102569726A (en) * 2010-12-30 2012-07-11 中国电子科技集团公司第十八研究所 Method for preparing lithium ion battery anode material coated with metal ions
CN102983313A (en) * 2012-12-05 2013-03-20 奇瑞汽车股份有限公司 Silicon-carbon composite material and preparation method thereof, and lithium ion battery
CN103346300A (en) * 2013-06-08 2013-10-09 合肥国轩高科动力能源股份公司 Method for in-situ synthesizing silicate/carbon composite cathode material by taking rice husk carbon as silicon source

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