CN103633305A - Silicon composite anode material of lithium ion battery and preparation method of silicon composite anode material - Google Patents

Silicon composite anode material of lithium ion battery and preparation method of silicon composite anode material Download PDF

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Publication number
CN103633305A
CN103633305A CN201310669739.7A CN201310669739A CN103633305A CN 103633305 A CN103633305 A CN 103633305A CN 201310669739 A CN201310669739 A CN 201310669739A CN 103633305 A CN103633305 A CN 103633305A
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silicon
metal
compound
preparation
oxide
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CN103633305B (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 silicon composite anode material of a lithium ion battery and a preparation method of the silicon composite anode material. The preparation method comprises the following steps: impregnating a precursor of a metal oxide with a porous biological silicon dioxide base body, drying, decomposing into a silicon dioxide and metal or nonmetal oxide compound, reducing silicon oxide and the metal oxide into silicon and metal at the same time by a magnesiothermic reaction, and washing through hydrochloric acid to obtain a silicon and metal or nonmetal compound. According to the composite material, metal is uniformly distributed in porous silicon, so that the silicon conductivity is improved; when the material serves as the anode material of the lithium ion battery, the metal or the nonmetal in the material serves as an inert material, has connecting and supporting effects on the silicon material and contributes to reduction of the expansion stress caused by the volume, so that the material has the advantages of high reversible capacity, good circulating performance and excellent rate performance.

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 is mainly used graphite material, but the theoretical capacity of graphite material (372 mAh/g), cannot meet the demand of height ratio capacity lithium ion, 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 discharging and recharging, produce larger effect of stress, make anodal differentiation degree serious, the intrinsic conductivity of silicon is lower in addition, is unfavorable for carrying out high power charging-discharging.Former studies is got up by the Material cladding of carbon and silicon, solves the application problem of above-mentioned silicium cathode material.Patent CN1909266A discloses a kind of method of a kind of copper silicon carbon composite of being prepared by high-energy ball milling, the composite material aperture obtaining 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 580 mAh/g left and right.And copper can not obtain very uniformly and mix with silicon.Advanced Materials magazine has been reported a kind of macropore silicon composite in 12 phase 1-4 in 2010.First with magnesiothermic reduction reaction, prepare the elemental silicon with three-dimensional structure, by silver mirror reaction depositing silver nano particle in macropore silicon, macropore silicon is mono-crystalline structures again, and its grain diameter is 1-5 micron, aperture is in 200 nanometer left and right, 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 thermal response, 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 dry, at high temperature resolve into silicon dioxide and metal composite, then utilize magnesium thermal response, oxygen reduction SiClx becomes silicon and metal with metal oxide simultaneously, then by chlorohydric acid pickling, obtains the compound of silicon and metal.
The technical scheme that the present invention needs protection is characterized by:
A preparation method for lithium ion battery silicon composite cathode material, is characterized in that, is the preparation method of silicon and metal composite, and 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) is obtained is heated to 300-850 degree Celsius in air, burns 2-6 hour, obtains the compound of porous silica and metal oxide.
Step 3: by step 2) compound obtaining after 1:0.1--20 mixes in mass ratio with magnesium powder, is heated to 600-850 degree Celsius in inert atmosphere, keeps 2-12 hour.
Step 4: after product that step 3) is obtained is cooling, immerse 0.2-6M(mol/L) aqueous hydrochloric acid solution, removes impurity, after filtration, clean and dry after obtain porous silicon and metallic composite.
Described metallic element can be to draw together copper, titanium or nickel, or their mixed form.
In step 1, described mesoporous silicon oxide predecessor, this raw material can be selected rice hull ash, diatomite or bagasse ash, or it mixes arbitrarily.
In step 1, the predecessor of described metal oxide is nitrate, chlorate or the acetate of titanium, copper and mickel, 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 be selected 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: porous silicon matrix and the metal being distributed in porous silicon pores, consist of, wherein metal and nonmetal silicon consists of 1-70 wt%, porous silicon matrix is polycrystalline structure, its grain diameter is at 5 nm-100 μ m, and aperture is at 0.001-5 μ m, 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 improve the conductance of silicon, this material is during as lithium ion battery negative material, and metal wherein, as inert material, rises and connects and supporting role silicon materials, contribute to alleviate the swelling stress that 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. raw material sources are abundant, cheap, and technique is simple.
2. in the duct in natural multiporous biological silicon dioxide, immerse metal oxide and through magnesium thermal response one step, be reduced into the compound of porous silicon and metal.
With metal composite after porous silicon, because electric conductivity and mechanical performance improve, it is during as ion cathode material lithium, capacity and preservation characteristics all obtain large increase.
Accompanying drawing explanation
Fig. 1. the present invention presses the electron microscope image of the copper/silicon compound of embodiment 1 acquisition.
Fig. 2. the present invention presses the elementary analysis of the copper/silicon compound of embodiment 1 acquisition.
Fig. 3. the present invention press embodiment 1 obtain copper/silicon compound with not with the contrast of the compound silicon circulation preservation characteristics of copper.
Fig. 4. the present invention presses copper/silicon compound that embodiment 1 obtains and the not contrast of the electrochemical impedance spectroscopy during as lithium ion cell electrode with the compound silicon of copper.
Embodiment
Below, by specific embodiment and accompanying drawing, technical solution of the present invention is described further, is verified.
embodiment 1
1) immersing concentration after diatomite is ground is 4M(mol/L) the aqueous solution of copper nitrate in, after its abundant absorbent solution, filter, dry.
2) mixture step 1) being 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 argon gas atmosphere, is incubated 7 hours,
4) after soaking 12 hours in the aqueous hydrochloric acid solution that is 2M by solid mixture in concentration after naturally cooling, filter, clean and dry, obtain the compound of copper/porous silicon.As shown in Figure 1 and Figure 2, final copper/the porous silicon composite material obtaining, its structure composition is characterized by: porous silicon matrix and the metal being distributed in porous silicon pores, consist of, wherein metal and the nonmetallic 1-70 wt% that consists of, porous silicon matrix is polycrystalline structure, its grain diameter is at 5 nm-100 μ m, and aperture is at 0.001-5 μ m, and hole is at 0.1-2.0 cm 3/ g, specific area is at 5-300 m 2/ g.
By the final copper/porous silicon composite material obtaining of step 4) and conductive agent (trade name: Super P) and the aqueous solution of sodium alginate according to 6:2:2(mass ratio) ratio be hybridly prepared into uniform slurry, by slurry coating on Copper Foil collection collector, after 120 degrees Celsius of vacuumize, be pressed into cathode pole piece, take metal lithium sheet as to electrode, the LiPF that the concentration of take is 1M 6the solution of ethylene carbonate, dimethyl carbonate and carbonic acid diethyl ester (1:1:1 v/v) be electrolyte, Celgard 2400 is barrier film, under dry inert atmosphere, is assembled into button cell, discharging and recharging by voltage is 5 mV-1.0 V.Discharging and recharging than under electric current of 1A/g, reversible capacity remains on 890 mAh/g. and not compound with copper porous silicon, and its specific capacity will be far smaller than this numerical value.As shown in Figure 4, the impedance analysis of electrode is also shown, the electrode being formed by copper/porous silicon composite material, its interfacial migration resistance is less than not the electrode that the porous silicon compound with copper forms.
embodiment 2
1) will rice hull ashafter grinding, immersing concentration is 0.01M(mol/L) the ethanolic solution of metatitanic acid four fourth fat in, after its abundant absorbent solution, filter, dry.
2) mixture step 1) being obtained under 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 argon gas atmosphere, is incubated 8 hours,
4) after soaking 12 hours in the aqueous hydrochloric acid solution that is 0.5M by solid mixture in concentration after naturally cooling, filter, clean and dry, obtain the compound of copper/porous silicon.
embodiment 3
1) will bagasse ashafter grinding, immersing concentration is 12M(mol/L) the aqueous solution of nickel acetate in, after its abundant absorbent solution, filter, dry.
2) mixture step 1) being obtained 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 argon gas atmosphere, is incubated 2 hours,
4) after soaking 12 hours in the aqueous hydrochloric acid solution that is 6M by solid mixture in concentration after naturally cooling, filter, clean and dry, obtain the compound of copper/porous silicon.

Claims (2)

1. a preparation method for lithium ion battery silicon composite cathode material, is characterized in that, is the preparation method of silicon and metal composite, and method step is followed successively by:
Step 1: mesoporous silicon oxide predecessor be impregnated in the precursor solution of 0.01 M--12 M metal oxide, after its abundant absorbent solution, filter, dry, obtain mixture;
Step 2: the mixture that step 1) is obtained is heated to 300-850 degree Celsius in air, burns 2-6 hour, obtains the compound of porous silica and metal oxide;
Step 3: by step 2) compound obtaining after 1:0.1--20 mixes in mass ratio with magnesium powder, is heated to 600-850 degree Celsius in inert atmosphere, keeps 2-12 hour;
Step 4: after product that step 3) is obtained is cooling, immerse the aqueous hydrochloric acid solution of 0.2-6M, remove impurity, after filtration, clean and dry after obtain porous silicon and metallic composite;
In step 1, described mesoporous silicon oxide predecessor, this raw material is selected rice hull ash, diatomite or bagasse ash, or it mixes arbitrarily;
In step 1, the predecessor of described metal oxide is nitrate, chlorate or the acetate of titanium, copper and mickel, or is metatitanic acid four fourth fat.
2. by claim 1 method, finally prepare end-product silicon/metallic composite, it is characterized in that, by porous silicon matrix and the metal being distributed in porous silicon pores, formed, wherein metal and nonmetal silicon consists of 1-70 wt%, porous silicon matrix is polycrystalline structure, its grain diameter is at 5 nm-100 μ m, and aperture is at 0.001-5 μ m, and hole is at 0.1-2.0 cm 3/ g, specific area is at 5-300 m 2/ g.
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Cited By (14)

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CN104157826A (en) * 2014-08-07 2014-11-19 国家电网公司 Preparation method of nano electrode negative electrode material
CN105006297A (en) * 2015-06-12 2015-10-28 安徽壹石通材料科技股份有限公司 Method for preparing conductive powder material based on soft silicon
CN105261792A (en) * 2015-07-21 2016-01-20 苏州迪思伏新能源科技有限公司 Preparation method for high-specific-energy secondary lithium ion battery with Si negative electrode and lithium- and manganese-rich positive electrode
CN105336934A (en) * 2015-11-21 2016-02-17 中国计量学院 Preparation method of silicon electrode composite material
CN105355888A (en) * 2015-11-21 2016-02-24 中国计量学院 Preparing method for nickel tin-carbon-silicon electrode material
CN105826528A (en) * 2016-03-22 2016-08-03 浙江大学 Porous silicon-copper composite material and preparation method and application thereof
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
CN108290740A (en) * 2015-11-25 2018-07-17 康宁股份有限公司 Porous silicon composition and device and its method
CN109562950A (en) * 2016-09-01 2019-04-02 复合材料技术公司 Nanoscale/nanostructure Si coating in the valve metal substrate of LIB anode
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
CN111874911A (en) * 2020-07-10 2020-11-03 同济大学 Preparation method of amorphous silicon material
WO2020253144A1 (en) * 2019-06-18 2020-12-24 Ningde Amperex Technology Limited Porous material and preparation methods thereof, and anodes and devices including the same
CN113224279A (en) * 2021-07-07 2021-08-06 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

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Cited By (24)

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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
CN104157826A (en) * 2014-08-07 2014-11-19 国家电网公司 Preparation method of nano electrode negative electrode material
CN105006297A (en) * 2015-06-12 2015-10-28 安徽壹石通材料科技股份有限公司 Method for preparing conductive powder material based on soft silicon
CN105261792A (en) * 2015-07-21 2016-01-20 苏州迪思伏新能源科技有限公司 Preparation method for high-specific-energy secondary lithium ion battery with Si negative electrode and lithium- and manganese-rich positive electrode
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
CN105336934A (en) * 2015-11-21 2016-02-17 中国计量学院 Preparation method of silicon electrode composite material
CN105355888A (en) * 2015-11-21 2016-02-24 中国计量学院 Preparing method for nickel tin-carbon-silicon electrode material
CN105336934B (en) * 2015-11-21 2017-10-20 中国计量学院 A kind of preparation method of silicon electrode composite
CN105355888B (en) * 2015-11-21 2018-02-06 中国计量学院 A kind of preparation method of nickel tin carbon-silicon electrodes material
CN108290740A (en) * 2015-11-25 2018-07-17 康宁股份有限公司 Porous silicon composition and device and its method
CN108290740B (en) * 2015-11-25 2022-03-04 康宁股份有限公司 Porous silicon composition and device and method thereof
US11139473B2 (en) 2015-11-25 2021-10-05 Corning Incorporated Porous silicon compositions and devices and methods thereof
CN105826528A (en) * 2016-03-22 2016-08-03 浙江大学 Porous silicon-copper composite material and preparation method and application thereof
CN105826528B (en) * 2016-03-22 2019-01-15 浙江大学 A kind of porous silicon-carbon/carbon-copper composite material and its preparation method and application
CN109562950A (en) * 2016-09-01 2019-04-02 复合材料技术公司 Nanoscale/nanostructure Si coating in the valve metal substrate of LIB anode
CN109562950B (en) * 2016-09-01 2020-05-19 复合材料技术公司 Nanoscale/nanostructured Si coatings on valve metal substrates for LIB anodes
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
WO2020253144A1 (en) * 2019-06-18 2020-12-24 Ningde Amperex Technology Limited Porous material and preparation methods thereof, and anodes and devices including the same
US11059724B2 (en) 2019-06-18 2021-07-13 Ningde Amperex Technology Limited Porous material and preparation methods thereof, and anodes and devices including the same
CN111874911A (en) * 2020-07-10 2020-11-03 同济大学 Preparation method of amorphous silicon material
CN113224279A (en) * 2021-07-07 2021-08-06 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
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

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