CN108321368A - A kind of polymer overmold silicon/lithium metasilicate negative material and preparation method thereof - Google Patents
A kind of polymer overmold silicon/lithium metasilicate negative material and preparation method thereof Download PDFInfo
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- CN108321368A CN108321368A CN201711461755.1A CN201711461755A CN108321368A CN 108321368 A CN108321368 A CN 108321368A CN 201711461755 A CN201711461755 A CN 201711461755A CN 108321368 A CN108321368 A CN 108321368A
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a kind of polymer overmold silicon/lithium metasilicate negative materials, are made of silicon/lithium metasilicate composite material and the polymer covering layer being coated on outside silicon/lithium metasilicate composite material；The polymer covering layer is a kind of clad of formation in polypyrrole, polyaniline, poly-dopamine or polyacrylonitrile.A kind of preparation method for polymer overmold silicon/lithium metasilicate negative material that the present invention also proposes, including：It prepares silicon/lithium metasilicate composite material and prepares polymer covering layer.Process of the present invention is simple for process, is convenient for large-scale production, degree of being practical is high, wherein obtained material reversible capacity is high, cycle performance is excellent, has broad application prospects in terms of negative electrode of lithium ion battery.
Description
Technical field
The present invention relates to lithium ion battery material technical field more particularly to a kind of polymer overmold silicon/lithium metasilicate are negative
Pole material and preparation method thereof.
Background technology
Silica-base material has its high specific capacity, such as the theoretical specific capacity of Si is 4200mAh/g, and SiO is
2000mAh/g is the ideal negative material of high-specific energy battery.But silica-base material has up in charge and discharge process
300% volume expansion, generates huge stress, causes the broken of silica-base material particle, so as to cause material dusting, finally
The cyclical stability of material is caused to decline.To solve this problem, academia takes nanometer silicon nitride material and structure compound, work
Industry is then taken matches binder and electrolyte with material (such as graphite) compounding of buffering silicon volume expansion or screening
Mode alleviate volume expansion and stable circulation sex chromosome mosaicism.
Currently, it solves the problems, such as that micron order silicon-based anode cyclical stability is poor and is also in the research starting stage, have no ten
Divide effective method.
Invention content
Technical problems based on background technology, the present invention propose a kind of polymer overmold silicon/lithium metasilicate cathode
Material and preparation method thereof, the preparation method process is simple, is convenient for large-scale production, degree of being practical is high, obtained cathode
Material can improve the coulombic efficiency for the first time of material while keeping high specific capacity, and can effectively improve the cycle of material
Performance.
A kind of polymer overmold silicon/lithium metasilicate negative material proposed by the present invention, by silicon/lithium metasilicate composite material
With the polymer covering layer composition being coated on outside silicon/lithium metasilicate composite material；
Wherein, the polymer covering layer is a kind of formation in polypyrrole, polyaniline, poly-dopamine or polyacrylonitrile
Clad.
Preferably, the silicon/weight content of the lithium metasilicate composite material in negative material is 95%-98%, polymerization
Weight content of the object clad in negative material is 2%-5%.
Preferably, particle size D50 is 5-10 μm.
A kind of preparation method for polymer overmold silicon/lithium metasilicate negative material that the present invention also proposes, including with
Lower step：
S1, silicon/lithium metasilicate composite material is prepared：The sub- silicon of oxidation and metallic lithium powder are taken, carries out ball milling under an argon atmosphere,
Obtain silicon/lithium metasilicate composite material；
S2, polymer covering layer is prepared：By the silicon in S1/lithium metasilicate composite material, conductive material and polymer monomer
It is dispersed in solvent, oxidizing agent solution progress polymerisation is added and obtains the polymer overmold silicon/lithium metasilicate cathode
Material.
Preferably, in S1, the grain size of the sub- silicon of oxidation is 3-10 μm；The grain size of the metallic lithium powder is 2-5 μm；Institute
The purity for stating argon gas is 99.99%；Si, O atom ratio are n, 1≤n in the sub- silicon of the oxidation<2.
Preferably, in S1, the sub- silicon of the oxidation, metallic lithium powder molar ratio be 8：1-4：2.
Preferably, in S1, Ball-milling Time 1-2h, the ball milling is mechanical ball mill.
Preferably, in S2, the conductive material is in conductive black, acetylene black, carbon nanotube, graphene, carbon fiber
One or more kinds of mixtures；The polymer monomer is one kind in pyrroles, aniline, dopamine or acrylonitrile；It is described
Solvent is one or two kinds of mixture in ethyl alcohol, water.
Preferably, in S2, the oxidizing agent solution is in ferric chloride solution, hydrogen peroxide solution, ammonium persulfate solution
One or more kinds of mixtures.
Preferably, a concentration of 0.1-1.0mol/L of the ferric chloride solution, hydrogen peroxide in the hydrogen peroxide solution
Mass fraction is 3%-10%；A concentration of 0.1-0.5mol/L of the ammonium persulfate solution.
The beneficial effects of the invention are as follows：Polymer is prepared for using the method that mechanical ball mill reaction and polymerized at normal temperature are combined
Coated Si/lithium metasilicate negative material；In the preparation process of negative material, sub- silicon is aoxidized by mixed with metallic lithium powder machinery
It closes, product silicon/lithium metasilicate of generation both maintains high power capacity, also improves the coulombic efficiency for the first time of material.Ball milling mistake simultaneously
Reaction forms Li in journey2SiO3Phase can improve Li+The volume expansion of ionic conduction and buffering silica-base material.Clad is by polymerizeing
Object forms, and effectively can connect and fetter active material particle.Therefore, this silicon/lithium metasilicate by polymer overmold
Negative material has higher specific capacity and for the first time coulombic efficiency and cycle performance is excellent.In addition, this preparation method is simple, peace
Entirely, at low cost, easily operated and industrialized production.
Description of the drawings
Fig. 1 is the structural schematic diagram of polymer overmold silicon/lithium metasilicate negative material proposed by the present invention；
Fig. 2 is the TEM pictures of polymer overmold silicon/lithium metasilicate negative material prepared by the embodiment of the present invention 1；
Fig. 3 is the XRD diagram piece of polymer overmold silicon/lithium metasilicate negative material prepared by the embodiment of the present invention 1；
Fig. 4 is the battery of the polymer overmold silicon/lithium metasilicate negative material assembling prepared using the embodiment of the present invention 1
First charge-discharge.
Specific implementation mode
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Fig. 1 is the structural schematic diagram of polymer overmold silicon/lithium metasilicate negative material proposed by the present invention；As shown in Figure 1,
It is made of silicon/lithium metasilicate composite material and the polymer covering layer being coated on outside silicon/lithium metasilicate composite material.
Embodiment 1
A kind of polymer overmold silicon/lithium metasilicate negative material that the present embodiment proposes, by silicon/lithium metasilicate composite wood
Expect (Si/Li2SiO3) and be coated on outside silicon/lithium metasilicate composite material polypyrrole clad (P) composition, wherein silicon/inclined silicon
Weight percent shared by sour lithium composite material is 95%, and the weight percent shared by polypyrrole clad is 5%, consisting of
[Si/Li2SiO3]0.95/P0.05；
A kind of preparation method for polymer overmold silicon/lithium metasilicate negative material that the present embodiment proposes, including with
Lower step：
S1, silicon/lithium metasilicate composite material Si/Li is prepared2SiO3：5.0g is aoxidized into sub- silicon and 0.5g metallic lithium powders in argon
Mechanical ball mill mixes 1h under gas atmosphere, obtains silicon/lithium metasilicate composite material Si/Li2SiO3；
S2, polypyrrole clad is prepared：By the silicon in 1.95g S1/lithium metasilicate composite material, 0.05g conductive materials and
200 μ L pyrroles are dispersed in 50ml ethyl alcohol, and the ferric chloride solution progress polymerisation that 6ml 0.5mol/L are added dropwise obtains institute
State polymer overmold silicon/lithium metasilicate negative material, i.e. polypyrrole coated Si/lithium metasilicate negative material.
Fig. 2 is the TEM pictures of polymer overmold silicon/lithium metasilicate negative material prepared by the embodiment of the present invention 1, by Fig. 2
It is found that core granule (central black region, about 1-1.5 μm) surface layer is coated with cotton-shaped polymer covering layer, clad table
Face is rough, there is abundant nanostructure.
Fig. 3 is the XRD diagram piece of polymer overmold silicon/lithium metasilicate negative material prepared by the embodiment of the present invention 1, by Fig. 3
It is found that the peak position of Si appears near 28.4,47.3 and 56.1 °, and Li2SiO3Diffraction maximum then 18.9,27.0,33.1,
Near 38.6 and 43.4 °.
Polypyrrole coated Si/lithium metasilicate negative material manufactured in the present embodiment and lithium are assembled into button electricity to electrode
Pond carries out first charge-discharge test to the button cell being assembled into, and the results are shown in Figure 4, as shown in Figure 4, uses the present invention
The first discharge specific capacity of battery of polymer overmold silicon prepared by embodiment 1/lithium metasilicate negative material assembling is
2146mAh/g, first charge-discharge efficiency 74.4%.
Embodiment 2
A kind of polymer overmold silicon/lithium metasilicate negative material that the present embodiment proposes, by silicon/lithium metasilicate composite wood
Expect (Si/Li2SiO3) and be coated on outside silicon/lithium metasilicate composite material polyaniline-coated layer (P) composition, wherein silicon/inclined silicon
Weight percent shared by sour lithium composite material is 95%, and the weight percent shared by polyaniline-coated layer is 5%, consisting of
[Si/Li2SiO3]0.95/P0.05；
A kind of preparation method for polymer overmold silicon/lithium metasilicate negative material that the present embodiment proposes, including with
Lower step：
S1, silicon/lithium metasilicate composite material Si/Li is prepared2SiO3：5.0g is aoxidized into sub- silicon and 0.5g metallic lithium powders in argon
Mechanical ball mill mixes 1h under gas atmosphere, obtains silicon/lithium metasilicate composite material Si/Li2SiO3；
S2, polyaniline-coated layer is prepared：By the silicon in 1.95g S1/lithium metasilicate composite material, 0.05g conductive materials and
200 μ L aniline are dispersed in 50ml ethyl alcohol, and the ferric chloride solution progress polymerisation that 6ml 0.5mol/L are added dropwise obtains institute
State polymer overmold silicon/lithium metasilicate negative material, i.e. polyaniline-coated silicon/lithium metasilicate negative material.
Polyaniline-coated silicon/lithium metasilicate negative material manufactured in the present embodiment and lithium are assembled into button electricity to electrode
Pond, the first discharge specific capacity for measuring battery are 2071mAh/g, first charge-discharge efficiency 68.5%.
Embodiment 3
A kind of polymer overmold silicon/lithium metasilicate negative material that the present embodiment proposes, by silicon/lithium metasilicate composite wood
Expect (Si/Li2SiO3) and be coated on outside silicon/lithium metasilicate composite material polypyrrole clad (P) composition, wherein silicon/inclined silicon
Weight percent shared by sour lithium composite material is 98%, and the weight percent shared by polypyrrole clad is 2%, consisting of
[Si/Li2SiO3]0.98/P0.02；
A kind of preparation method for polymer overmold silicon/lithium metasilicate negative material that the present embodiment proposes, including with
Lower step：
S1, silicon/lithium metasilicate composite material Si/Li is prepared2SiO3：5.0g is aoxidized into sub- silicon and 0.5g metallic lithium powders in argon
Mechanical ball mill mixes 0.5h under gas atmosphere, obtains silicon/lithium metasilicate composite material Si/Li2SiO3；
S2, polymer covering layer is prepared：By the silicon in 1.95g S1/lithium metasilicate composite material, 0.05g conductive materials and
80 μ L pyrroles are dispersed in 50ml ethyl alcohol, and the ammonium persulfate solution progress polymerisation that 15ml 0.1mol/L are added dropwise obtains
Polymer overmold silicon/lithium metasilicate the negative material, i.e. polypyrrole coated Si/lithium metasilicate negative material.
Polypyrrole coated Si/lithium metasilicate negative material manufactured in the present embodiment and lithium are assembled into button electricity to electrode
Pond, the first discharge specific capacity for measuring battery are 2096mAh/g, first charge-discharge efficiency 71.4%.
Embodiment 4
A kind of polymer overmold silicon/lithium metasilicate negative material that the present embodiment proposes, by silicon/lithium metasilicate composite wood
Expect (Si/Li2SiO3) and be coated on outside silicon/lithium metasilicate composite material polyaniline-coated layer (P) composition, wherein silicon/inclined silicon
Weight percent shared by sour lithium composite material is 98%, and the weight percent shared by polyaniline-coated layer is 2%, consisting of
[Si/Li2SiO3]0.98/P0.02；
A kind of preparation method for polymer overmold silicon/lithium metasilicate negative material that the present embodiment proposes, including with
Lower step：
S1, silicon/lithium metasilicate composite material Si/Li is prepared2SiO3：5.0g is aoxidized into sub- silicon and 0.5g metallic lithium powders in argon
Mechanical ball mill mixes 0.5h under gas atmosphere, obtains silicon/lithium metasilicate composite material Si/Li2SiO3；
S2, polymer covering layer is prepared：By the silicon in 1.95g S1/lithium metasilicate composite material, 0.05g conductive materials and
80 μ L aniline are dispersed in 50ml ethyl alcohol, and the ammonium persulfate solution progress polymerisation that 15ml 0.1mol/L are added dropwise obtains
Polymer overmold silicon/lithium metasilicate the negative material, i.e. polyaniline-coated silicon/lithium metasilicate negative material.
Polyaniline-coated silicon/lithium metasilicate negative material manufactured in the present embodiment and lithium are assembled into button electricity to electrode
Pond, the first discharge specific capacity for measuring battery are 1804mAh/g, first charge-discharge efficiency 54.6%.
Embodiment 5
A kind of polymer overmold silicon/lithium metasilicate negative material proposed by the present invention, by silicon/lithium metasilicate composite material
With the polymer covering layer composition being coated on outside silicon/lithium metasilicate composite material；
Wherein, the polymer covering layer is the clad that polypyrrole is formed.
A kind of preparation method for polymer overmold silicon/lithium metasilicate negative material that the present invention also proposes, including with
Lower step：
S1, silicon/lithium metasilicate composite material is prepared：The sub- silicon of oxidation and metallic lithium powder are taken, carries out ball milling under an argon atmosphere,
Obtain silicon/lithium metasilicate composite material；
S2, polymer covering layer is prepared：By the silicon in S1/lithium metasilicate composite material, conductive material and polymer monomer
It is dispersed in solvent, oxidizing agent solution progress polymerisation is added and obtains the polymer overmold silicon/lithium metasilicate cathode
Material.
Embodiment 6
A kind of polymer overmold silicon/lithium metasilicate negative material proposed by the present invention, by silicon/lithium metasilicate composite material
With the polymer covering layer composition being coated on outside silicon/lithium metasilicate composite material；
Wherein, the silicon/weight content of the lithium metasilicate composite material in negative material is 98%, polymer covering layer
Weight content in negative material is 2%；The polymer covering layer is the clad that polypyrrole is formed；The polymer packet
The particle size D50 for covering silicon/lithium metasilicate negative material is 5 μm.
A kind of preparation method for polymer overmold silicon/lithium metasilicate negative material that the present invention also proposes, including with
Lower step：
S1, silicon/lithium metasilicate composite material is prepared：The sub- silicon of oxidation and metallic lithium powder are taken, carries out ball milling under an argon atmosphere
1h obtains silicon/lithium metasilicate composite material；Wherein, the grain size of the sub- silicon of the oxidation is 3-10 μm；The grain size of the metallic lithium powder
It is 2-5 μm；The purity of the argon gas is 99.99%；Si, O atom ratio are n, n=1 in the sub- silicon of the oxidation；The oxidation is sub-
Silicon, metallic lithium powder molar ratio be 8：1；The ball milling is mechanical ball mill；
S2, polymer covering layer is prepared：By the silicon in S1/lithium metasilicate composite material, conductive material and polymer monomer
It is dispersed in solvent, oxidizing agent solution progress polymerisation is added and obtains the polymer overmold silicon/lithium metasilicate cathode
Material；Wherein, the conductive material is the mixture of acetylene black, carbon nanotube, and the mass ratio of acetylene black, carbon nanotube is 3:
2；The polymer monomer is pyrroles；The solvent is ethyl alcohol；The oxidizing agent solution is ferric chloride solution；The iron chloride is molten
A concentration of 0.1mol/L of liquid.
Embodiment 7
A kind of polymer overmold silicon/lithium metasilicate negative material proposed by the present invention, by silicon/lithium metasilicate composite material
With the polymer covering layer composition being coated on outside silicon/lithium metasilicate composite material；
Wherein, the silicon/weight content of the lithium metasilicate composite material in negative material is 95%, polymer covering layer
Weight content in negative material is 5%；The polymer covering layer is the clad that polyaniline is formed；The polymer packet
The particle size D50 for covering silicon/lithium metasilicate negative material is 10 μm.
A kind of preparation method for polymer overmold silicon/lithium metasilicate negative material that the present invention also proposes, including with
Lower step：
S1, silicon/lithium metasilicate composite material is prepared：The sub- silicon of oxidation and metallic lithium powder are taken, carries out ball milling under an argon atmosphere
2h obtains silicon/lithium metasilicate composite material；Wherein, the grain size of the sub- silicon of the oxidation is 3-10 μm；The grain size of the metallic lithium powder
It is 2-5 μm；The purity of the argon gas is 99.99%；Si, O atom ratio are n, n=1.8 in the sub- silicon of the oxidation；The oxidation is sub-
Silicon, metallic lithium powder molar ratio be 4：2；The ball milling is mechanical ball mill；
S2, polymer covering layer is prepared：By the silicon in S1/lithium metasilicate composite material, conductive material and polymer monomer
It is dispersed in solvent, oxidizing agent solution progress polymerisation is added and obtains the polymer overmold silicon/lithium metasilicate cathode
Material；Wherein, the conductive material is conductive black；The polymer monomer is aniline；The solvent is water；The oxidant
Solution is hydrogen peroxide solution；The mass fraction of hydrogen peroxide is 3% in the hydrogen peroxide solution.
Embodiment 8
A kind of polymer overmold silicon/lithium metasilicate negative material proposed by the present invention, by silicon/lithium metasilicate composite material
With the polymer covering layer composition being coated on outside silicon/lithium metasilicate composite material；
Wherein, the silicon/weight content of the lithium metasilicate composite material in negative material is 97%, polymer covering layer
Weight content in negative material is 3%；The polymer covering layer is the clad that poly-dopamine is formed；The polymer
The particle size D50 of coated Si/lithium metasilicate negative material is 8 μm.
A kind of preparation method for polymer overmold silicon/lithium metasilicate negative material that the present invention also proposes, including with
Lower step：
S1, silicon/lithium metasilicate composite material is prepared：The sub- silicon of oxidation and metallic lithium powder are taken, carries out ball milling under an argon atmosphere
1.5h obtains silicon/lithium metasilicate composite material；Wherein, the grain size of the sub- silicon of the oxidation is 3-10 μm；The grain of the metallic lithium powder
Diameter is 2-5 μm；The purity of the argon gas is 99.99%；Si, O atom ratio are n, n=1.5 in the sub- silicon of the oxidation；The oxidation
Sub- silicon, metallic lithium powder molar ratio be 5：1；The ball milling is mechanical ball mill；
S2, polymer covering layer is prepared：By the silicon in S1/lithium metasilicate composite material, conductive material and polymer monomer
It is dispersed in solvent, oxidizing agent solution progress polymerisation is added and obtains the polymer overmold silicon/lithium metasilicate cathode
Material；Wherein, the conductive material is the mixture of conductive black, graphene, carbon fiber, and conductive black, graphene, carbon fiber
The mass ratio of dimension is 4:3:2；The polymer monomer is dopamine；The solvent is the mixture of ethyl alcohol, water, and ethyl alcohol, water
Volume ratio be 3:2；The oxidizing agent solution is the mixture of ferric chloride solution, hydrogen peroxide solution, ammonium persulfate solution；It is described
A concentration of 1.0mol/L of ferric chloride solution, the mass fraction of hydrogen peroxide is 10% in the hydrogen peroxide solution；The over cure
A concentration of 0.5mol/L of acid ammonium solution.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of polymer overmold silicon/lithium metasilicate negative material, which is characterized in that its by silicon/lithium metasilicate composite material and
The polymer covering layer composition being coated on outside silicon/lithium metasilicate composite material；
Wherein, the polymer covering layer is a kind of packet of formation in polypyrrole, polyaniline, poly-dopamine or polyacrylonitrile
Coating.
2. polymer overmold silicon/lithium metasilicate negative material according to claim 1, which is characterized in that the silicon/metasilicic acid
Weight content of the lithium composite material in negative material is 95%-98%, and weight of the polymer covering layer in negative material contains
Amount is 2%-5%.
3. polymer overmold silicon/lithium metasilicate negative material according to claim 1 or claim 2, which is characterized in that its particle size
D50 is 5-10 μm.
4. a kind of preparation method of polymer overmold silicon/lithium metasilicate negative material as described in any one of claim 1-3,
It is characterized in that, includes the following steps：
S1, silicon/lithium metasilicate composite material is prepared：The sub- silicon of oxidation and metallic lithium powder are taken, ball milling is carried out under an argon atmosphere, obtains
Silicon/lithium metasilicate composite material；
S2, polymer covering layer is prepared：Silicon in S1/lithium metasilicate composite material, conductive material and polymer monomer is uniform
It is scattered in solvent, oxidizing agent solution progress polymerisation is added and obtains the polymer overmold silicon/lithium metasilicate negative material.
5. the preparation method of polymer overmold silicon/lithium metasilicate negative material according to claim 4, which is characterized in that
In S1, the grain size of the sub- silicon of oxidation is 3-10 μm；The grain size of the metallic lithium powder is 2-5 μm；The purity of the argon gas is
99.99%；Si, O atom ratio are n, 1≤n in the sub- silicon of the oxidation<2.
6. the preparation method of the polymer overmold silicon/lithium metasilicate negative material according to claim 4 or 5, which is characterized in that
In S1, the sub- silicon of the oxidation, metallic lithium powder molar ratio be 8：1-4：2.
7. special according to the preparation method of any one of the claim 4-6 polymer overmold silicon/lithium metasilicate negative materials
Sign is, in S1, Ball-milling Time 1-2h, the ball milling is mechanical ball mill.
8. special according to the preparation method of any one of the claim 4-7 polymer overmold silicon/lithium metasilicate negative materials
Sign is, in S2, the conductive material be conductive black, acetylene black, carbon nanotube, graphene, one kind in carbon fiber or
The a variety of mixture of person；The polymer monomer is one kind in pyrroles, aniline, dopamine or acrylonitrile；The solvent is second
One or two kinds of mixture in alcohol, water.
9. special according to the preparation method of any one of the claim 4-8 polymer overmold silicon/lithium metasilicate negative materials
Sign is, in S2, the oxidizing agent solution be ferric chloride solution, hydrogen peroxide solution, one kind in ammonium persulfate solution or
A variety of mixtures.
10. the preparation method of polymer overmold silicon/lithium metasilicate negative material according to claim 9, which is characterized in that institute
State a concentration of 0.1-1.0mol/L of ferric chloride solution, the mass fraction of hydrogen peroxide is 3%- in the hydrogen peroxide solution
10%；A concentration of 0.1-0.5mol/L of the ammonium persulfate solution.
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| EP3945612A1 (en) * | 2020-07-29 | 2022-02-02 | SK Innovation Co., Ltd. | Lithium-doped silicon-based oxide negative electrode active material, method of preparing the same, and negative electrode and secondary battery including the same |
| CN114937765A (en) * | 2022-05-27 | 2022-08-23 | 山东海科创新研究院有限公司 | Modified polyimide-coated silicon/lithium silicate negative electrode material, preparation method thereof and lithium ion battery |
| CN114937765B (en) * | 2022-05-27 | 2024-04-19 | 山东海科创新研究院有限公司 | Modified polyimide coated silicon/lithium silicate negative electrode material, preparation method thereof and lithium ion battery |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1407641A (en) * | 2001-09-05 | 2003-04-02 | 信越化学工业株式会社 | Monox powder containing Li and its manufacture |
| CN1850597A (en) * | 2006-04-28 | 2006-10-25 | 中国科学院上海硅酸盐研究所 | Method for preparig lithium secondary cell silicon/rich-lithium phase composite cathode material by high energy ball milling |
| CN101304088A (en) * | 2008-06-27 | 2008-11-12 | 三峡大学 | Method for preparing sphericity lithium ion battery silicon/stannum binary lithium-storing precursor composite cathode material |
| CN103400971A (en) * | 2013-07-29 | 2013-11-20 | 宁德新能源科技有限公司 | Silicon-based composite material and preparation method and applications thereof |
| CN103474631A (en) * | 2013-10-08 | 2013-12-25 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon monoxide composite negative electrode material for lithium ion battery, preparation method and lithium ion battery |
| CN103700816A (en) * | 2013-12-12 | 2014-04-02 | 天津巴莫科技股份有限公司 | Preparation method of silicon-based composite of lithium ion battery |
| CN104022282A (en) * | 2014-05-27 | 2014-09-03 | 华南理工大学 | High temperature solid state preparation method of lithium ion battery cathode material lithium metasilicate |
| CN104157875A (en) * | 2014-06-10 | 2014-11-19 | 西北师范大学 | Method for preparing nanometer silicon conductive polymer composite material for lithium ion batteries |
| CN105140486A (en) * | 2015-08-31 | 2015-12-09 | 无锡市嘉邦电力管道厂 | High-capacity lithium ion battery anode material and preparing method thereof |
| CN105514378A (en) * | 2015-12-22 | 2016-04-20 | 湘潭大学 | Lithium-sulfur battery positive-pole composite material with imitated cellular structure and preparation method thereof |
| CN106058167A (en) * | 2016-02-03 | 2016-10-26 | 万向A二三***有限公司 | Porous silicon-based alloy composite |
| CN106229495A (en) * | 2016-09-30 | 2016-12-14 | 深圳大学 | A kind of silicon based anode material of conducting polymer cladding and preparation method thereof |
| CN106252638A (en) * | 2016-10-11 | 2016-12-21 | 大连海事大学 | A kind of silicon/oxide composite negative pole material with Lithium metasilicate boundary layer and preparation method |
| CN106711431A (en) * | 2016-12-31 | 2017-05-24 | 武汉理工大学 | Silicon-base cathode material for lithium ion battery and preparation method of silicon-base cathode material |
| CN106816594A (en) * | 2017-03-06 | 2017-06-09 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of compound, its preparation method and the purposes in lithium rechargeable battery |
| CN107195867A (en) * | 2016-03-15 | 2017-09-22 | 宁德新能源科技有限公司 | Negative active core-shell material and preparation method thereof and secondary cell |
| CN107195896A (en) * | 2017-04-06 | 2017-09-22 | 中国计量大学 | A kind of preparation method that silicium cathode material is synthesized by carrier low temperature of conducting metal nano particle |
| CN107210435A (en) * | 2015-01-28 | 2017-09-26 | 三洋电机株式会社 | Anode for nonaqueous electrolyte secondary battery active material and rechargeable nonaqueous electrolytic battery |
-
2017
- 2017-12-28 CN CN201711461755.1A patent/CN108321368B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1407641A (en) * | 2001-09-05 | 2003-04-02 | 信越化学工业株式会社 | Monox powder containing Li and its manufacture |
| CN1850597A (en) * | 2006-04-28 | 2006-10-25 | 中国科学院上海硅酸盐研究所 | Method for preparig lithium secondary cell silicon/rich-lithium phase composite cathode material by high energy ball milling |
| CN101304088A (en) * | 2008-06-27 | 2008-11-12 | 三峡大学 | Method for preparing sphericity lithium ion battery silicon/stannum binary lithium-storing precursor composite cathode material |
| CN103400971A (en) * | 2013-07-29 | 2013-11-20 | 宁德新能源科技有限公司 | Silicon-based composite material and preparation method and applications thereof |
| CN103474631A (en) * | 2013-10-08 | 2013-12-25 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon monoxide composite negative electrode material for lithium ion battery, preparation method and lithium ion battery |
| CN103700816A (en) * | 2013-12-12 | 2014-04-02 | 天津巴莫科技股份有限公司 | Preparation method of silicon-based composite of lithium ion battery |
| CN104022282A (en) * | 2014-05-27 | 2014-09-03 | 华南理工大学 | High temperature solid state preparation method of lithium ion battery cathode material lithium metasilicate |
| CN104157875A (en) * | 2014-06-10 | 2014-11-19 | 西北师范大学 | Method for preparing nanometer silicon conductive polymer composite material for lithium ion batteries |
| CN107210435A (en) * | 2015-01-28 | 2017-09-26 | 三洋电机株式会社 | Anode for nonaqueous electrolyte secondary battery active material and rechargeable nonaqueous electrolytic battery |
| CN105140486A (en) * | 2015-08-31 | 2015-12-09 | 无锡市嘉邦电力管道厂 | High-capacity lithium ion battery anode material and preparing method thereof |
| CN105514378A (en) * | 2015-12-22 | 2016-04-20 | 湘潭大学 | Lithium-sulfur battery positive-pole composite material with imitated cellular structure and preparation method thereof |
| CN106058167A (en) * | 2016-02-03 | 2016-10-26 | 万向A二三***有限公司 | Porous silicon-based alloy composite |
| CN107195867A (en) * | 2016-03-15 | 2017-09-22 | 宁德新能源科技有限公司 | Negative active core-shell material and preparation method thereof and secondary cell |
| CN106229495A (en) * | 2016-09-30 | 2016-12-14 | 深圳大学 | A kind of silicon based anode material of conducting polymer cladding and preparation method thereof |
| CN106252638A (en) * | 2016-10-11 | 2016-12-21 | 大连海事大学 | A kind of silicon/oxide composite negative pole material with Lithium metasilicate boundary layer and preparation method |
| CN106711431A (en) * | 2016-12-31 | 2017-05-24 | 武汉理工大学 | Silicon-base cathode material for lithium ion battery and preparation method of silicon-base cathode material |
| CN106816594A (en) * | 2017-03-06 | 2017-06-09 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of compound, its preparation method and the purposes in lithium rechargeable battery |
| CN107195896A (en) * | 2017-04-06 | 2017-09-22 | 中国计量大学 | A kind of preparation method that silicium cathode material is synthesized by carrier low temperature of conducting metal nano particle |
Non-Patent Citations (3)
| Title |
|---|
| JEE HO YOM: ""Improvement of irreversible behavior of SiO anodes for lithium ion batteries by a solid state reaction at high temperature"", 《JOURNAL OF POWER SOURCES》 * |
| XUELIN YANG: ""Nanosized silicon-based composite derived by in situ mechanochemical reduction for lithium ion batteries"", 《JOURNAL OF POWER SOURCES》 * |
| YOON HWA: ""Modified SiO as a high performance anode for Li-ion batteries"", 《JOURNAL OF POWER SOURCES》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109286012A (en) * | 2018-09-29 | 2019-01-29 | 北京科技大学 | A kind of high magnification aoxidizes the preparation method of sub- silicon substrate lithium cell negative pole material |
| CN109286012B (en) * | 2018-09-29 | 2021-01-05 | 北京科技大学 | Preparation method of high-rate silica-based lithium battery negative electrode material |
| CN109494360A (en) * | 2018-10-26 | 2019-03-19 | 合肥国轩高科动力能源有限公司 | A kind of oxidation Asia silicon composite and preparation method thereof |
| CN109728281B (en) * | 2018-12-31 | 2021-10-12 | 青岛农业大学 | Preparation method of surface modified SiOx electrode material |
| CN109728281A (en) * | 2018-12-31 | 2019-05-07 | 青岛农业大学 | A kind of preparation method of the modified SiOx electrode material in surface |
| CN111584831B (en) * | 2019-02-15 | 2022-10-28 | 江西格林德能源有限公司 | Polymer-coated silicon/sulfur-doped graphene negative electrode material and preparation method thereof |
| CN111584831A (en) * | 2019-02-15 | 2020-08-25 | 江西格林德能源有限公司 | Polymer-coated silicon/sulfur-doped graphene negative electrode material and preparation method thereof |
| US11223041B2 (en) | 2019-02-20 | 2022-01-11 | Ningde Amperex Technology Limited | Anode active material and anode, electrochemical device and electronic device using the same |
| WO2020168785A1 (en) * | 2019-02-20 | 2020-08-27 | Ningde Amperex Technology Limited | Anode active material and anode, electrochemical device and electronic device using the same |
| CN111146421A (en) * | 2019-12-26 | 2020-05-12 | 宁德新能源科技有限公司 | Negative electrode material, and electrochemical device and electronic device comprising same |
| EP3945612A1 (en) * | 2020-07-29 | 2022-02-02 | SK Innovation Co., Ltd. | Lithium-doped silicon-based oxide negative electrode active material, method of preparing the same, and negative electrode and secondary battery including the same |
| US11923540B2 (en) | 2020-07-29 | 2024-03-05 | Sk On Co., Ltd. | Lithium-doped silicon-based oxide negative electrode active material, method of preparing the same, and negative electrode and secondary battery including the same |
| CN112467114A (en) * | 2020-11-30 | 2021-03-09 | 湖南中科星城石墨有限公司 | Silica composite material, preparation method thereof and lithium ion battery |
| CN113036108A (en) * | 2021-03-11 | 2021-06-25 | 昆山宝创新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN113130868A (en) * | 2021-04-09 | 2021-07-16 | 昆山宝创新能源科技有限公司 | Composite material containing silicon monoxide, negative plate, lithium battery and preparation method thereof |
| CN113611860A (en) * | 2021-07-13 | 2021-11-05 | 欣旺达电动汽车电池有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
| CN114937765A (en) * | 2022-05-27 | 2022-08-23 | 山东海科创新研究院有限公司 | Modified polyimide-coated silicon/lithium silicate negative electrode material, preparation method thereof and lithium ion battery |
| CN114937765B (en) * | 2022-05-27 | 2024-04-19 | 山东海科创新研究院有限公司 | Modified polyimide coated silicon/lithium silicate negative electrode material, preparation method thereof and lithium ion battery |
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