CN104393299A - Nanometer silicon-polythiophene electric conduction composite material for lithium ion battery, and preparation method thereof - Google Patents
Nanometer silicon-polythiophene electric conduction composite material for lithium ion battery, and preparation method thereof Download PDFInfo
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- CN104393299A CN104393299A CN201410489470.9A CN201410489470A CN104393299A CN 104393299 A CN104393299 A CN 104393299A CN 201410489470 A CN201410489470 A CN 201410489470A CN 104393299 A CN104393299 A CN 104393299A
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
Abstract
The present invention provides a nanometer silicon-polythiophene electric conduction composite material, and belongs to the technical field of lithium ion batteries. According to the present invention, nanometer silicon is adopted as a lithium-embedded active material, thiophene is adopted as an electric conduction monomer, chloroform is adopted as a solvent, anhydrous ferric chloride is adopted as an oxidant, and chemical oxidation in situ polymerization is performed to obtain the nanometer silicon-polythiophene electric conduction composite material, wherein in the composite material, the electric conduction polythiophene is uniformly coated on the surface of the silicon nanoparticles, and the nanometer silicon particles have the lithium storage activity, such that the cycle performance of the silicon base electrode material are improved with the electric conduction polythiophene from the two sides of the volume effect and the electric conductivity; and experiment results show that the lithium ion battery prepared from the nanometer silicon-polythiophene electric conduction composite material has the following characteristics that: the initial discharge specific capacity is about 2300 mAh/g, and the specific capacity is maintained at 501 mAh/g after 50 charge-discharge tests, such that the good electrochemical cycle performance is provided, and the good prospect is provided in practical applications.
Description
Technical field
The invention belongs to technical field of lithium ion, relate to a kind of silica-base material for lithium ion battery negative material; Particularly relate to a kind of nano-silicon-polythiophene composite material and preparation method thereof.
Background technology
Along with the development of science and technology and the progressive energy crisis of the mankind and environmental pollution cause the extensive attention of people; traditional energy not only reserves is limited; belong to non-renewable energy resources, and environmental pollution is serious, association area scientist is actively finding new forms of energy always.In recent years, power-type lithium ion battery causes the attention of researcher.Current business-like lithium ion battery negative material is theoretical specific capacity lower (372 mAh/g) graphite mainly, can not meet the requirement of high-power electric appliance far away.So, as silica-based, tinbase etc., there is the extensive concern that high theoretical specific capacity electrode material causes scientist.Silica-base material is a kind of material (4200 mAh/g) that in the various alloy type materials of research at present, theoretical specific capacity is the highest.But change in volume very large (reaching 420%), causes silicon nanostructure material powder fragility to be destroyed, newly sharply declining of battery in embedding lithium process.Therefore, at present the conductivity aspect reduced because of the bulk effect in charge and discharge process and increase silica-base material is mainly concentrated on to the research of silica-base material.The main method improving silica-base material performance has: nanometer, Composite, employing novel binders, improve collector and electrolyte, and nanometer to combine with Composite be the major way that silica-base material is studied.
Since the U.S. in 2000 and Japanese Scientists obtain Nobel chemistry Prize because finding conducting polymer, the application study of conducting polymer in electrode material is more and more deep.The conductivity that conducting polymer not only can increase material is introduced in the preparation process of silicon based electrode material, but also the change in volume of the silicon grain in charge and discharge process can be reduced, improve the cyclical stability of silica-base material largely, improve the performance of battery.
Summary of the invention
The object of the invention is to solve the subproblem existed in prior art, having prepared a kind of nano-silicon-polythiophene composite material for lithium ion battery negative material.
Another object of the present invention is to provide a kind of preparation method of above-mentioned nano-silicon-polythiophene composite material for lithium ion battery negative material.
One, the preparation of nano-silicon-polythiophene composite material
Nano-silicon-polythiophene composite material of the present invention is at the outer even coated one deck conductive polythiophene of silicon nanoparticle.In order to farthest improve the cycle performance of silica-base material, control 7.5 ~ 34.2% by the mass percent of polythiophene in composite material, the mass percent of active material silicon nanoparticle controls 65.8 ~ 92.5%.
The preparation method of nano-silicon-polythiophene composite material of the present invention is: be first that silicon grain and the oxidant ferric trichloride of 20 ~ 160nm is scattered in chloroform by particle diameter, the polymerization single polymerization monomer thiophene dissolved with ethanol is added, in polymerized at room temperature reaction 3 ~ 20h under stirring after stirring; Reaction terminates rear suction filtration, and successively by absolute ethyl alcohol, hydrochloric acid, deionized water washing extremely neutrality, vacuumize, grinds and get final product.
The mass ratio of silicon nanoparticle and thiophene monomer is 9:1 ~ 1:1; The mol ratio of ferric trichloride and thiophene monomer is 2:1 ~ 6:1.
In nano-silicon polymer composites of the present invention, it is active that silicon nanoparticle has storage lithium, and conductive polythiophene improves the cycle performance of silicon based electrode material on both side from bulk effect and conductivity.
Two, the structural characterization of nano-silicon polymer composites
1, infrared spectrum analysis
Fig. 1 is the infrared spectrogram of Si, PTh/Si, PTh of the present invention.As can be seen from Figure 1,784 cm
-12,5-dibasic polythiophene C-H out-of-plane bending vibration absworption peak, 1109 cm
-1the C-H stretching vibration absworption peak of thiphene ring, 1028 cm
-1, 692cm
-1the asymmetric of C-S and symmetrical stretching vibration absworption peak respectively, 1319 cm
-1it is the asymmetric stretching vibration absworption peak of C-C.784 cm
-1the oxidation polymerization of thiophene occurs in α position to have absworption peak to illustrate, the polymerization of α position has good conductivity than the polythiophene of β position polymerization.
2, XRD spectra analysis
The XRD collection of illustrative plates of composite material nanometer silicon-polythiophene (Si/ PTh), polythiophene (PTh) and the Si of Fig. 2 prepared by the present invention.The spectrogram of silicon as can be seen from Fig. 2,2 θ=28.4 °, (111), (220), (311) of 47.2 °, 56.1 °, 69.1 ° and the 76.3 ° corresponding silicon of difference, (400) and (331) crystallographic plane diffraction peak.Si/ PTh composite material only shows the crystallographic plane diffraction peak of elemental silicon, illustrates that the polythiophene prepared is completely unbodied.
3, thermal weight loss (TG) is analyzed
The thermogravimetric curve figure of the composite material of Fig. 3 prepared by the present invention under moving air component.As can be seen from Figure 3, mass ratio shared by rate of charge thiophene monomer is 10 wt.%, 20 wt.%, 30 wt.%, 40 wt.% and 50 wt.% reality only coated upper 1.0 wt.%, 7.5 wt.%, 15.2 wt.%, 25.2 wt.% and 34.2 wt.% respectively, the temperature range of test is that room temperature is to 800 DEG C, test under moving air component, programming rate is 10 DEG C/min.Can find out that from curve thiophene monomer only has part generation oxidation polymerization.Illustrate that Si/ PTh composite material has good thermal stability.
4, scanning electron microscope analysis
The scanning electron microscope (SEM) photograph of Fig. 4 silica-base material prepared by the present invention, the SEM of the SEM of (a) Si, (b) Si/ PTh.Comparison diagram a, b, be coated on the surface of nano silicon particles after can obviously seeing thiophene polymeric uniformly.
5, TEM (transmission electron microscope) analysis
The transmission of Fig. 5 composite material prepared by the present invention and scanning transmission electron microscope figure.A () is the transmission electron microscope picture of composite material Si/PTh, the scanning transmission electron microscope figure of (b) composite material Si/ PTh.What a in () figure, color was more shallow is polythiophene, and color is comparatively dark and what have diffraction decorative pattern is silicon nanoparticle; B in () figure, the bright spot of white is silicon nanoparticle, the darker material of bright spot ambient color is conductive polythiophene.Be proven further from Fig. 5, the coated uniformly surface of silicon grain after thiophene polymeric.
Three, the electrochemical property test of nano-silicon conductive voltolisation thiophene composite
Using the silicon polythiophene composite material for preparing in mass ratio: composite material: conductive acetylene is black: the ratio of binding agent=70:20:10 on Copper Foil smear as electrode material with lithium sheet for be made into button cell to electrode.Carry out the test of electrochemistry cycle performance with the current density of 100mA/g, carry out 100 charge-discharge tests to it, test voltage interval is 0.02 ~ 1.5V.
1, cycle performance test analysis
The electrochemistry cycle performance figure of Fig. 6 electrode material prepared by the present invention.As can be seen from the cyclic curve in Fig. 6, pure nano-silicon electrode due in charge and discharge process change in volume comparatively large, occur structural pulverizing, circulation newly can be die-offed; Nano-silicon-polythiophene electrode material is significantly improved compared to pure silicon electrode cycle performance: first charge-discharge coulombic efficiency reaches 77.9%, after 50 circulations, specific capacity is still close to 501 mAh/g, very fast at front 10 special capacity fades of circulation, circulation afterwards shows good cyclical stability.
2, cyclic voltammetry analysis
Fig. 7 is the cyclic voltammogram of electrode material under 0.1mv sweeps speed prepared by the present invention.As can be seen from the curve of Fig. 7; an obvious peak is had at 0.4 V place first in discharge process; mainly to form a solid electrolyte diaphragm (SEI) due in embedding lithium process first, the corrosion of the electrolyte decomposition that the circulation after can preventing occurs with direct contact of electrolyte due to electrode material and nano-silicon.Lithium ion and elemental silicon obtain the process that electronics forms Li-Si alloy and create reduction peak; The process that Li-Si alloy loses electronics formation lithium ion and elemental silicon creates oxidation peak, and first time differs greatly with second time cyclic curve, and second time reduces with third time circulation difference, illustrates that the cycle performance of electrode material more and more tends towards stability.
In sum, nano-silicon-polythiophene composite material that prepared by the present invention has embodied good cycle performance.Coating layer polythiophene improves the performance of electrode material on both side from bulk effect and conductivity, its specific capacity is far away higher than the theoretical specific capacity of current commercialization negative material graphite, and the preparation technology of electrode material is simple, environmentally friendly, in future, there is Commercial Prospect.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of Si, PTh/Si, PTh of the present invention;
The XRD collection of illustrative plates of Fig. 2 material Si/ PTh, PTh and Si prepared by the present invention;
The thermogravimetric curve figure of the composite material of Fig. 3 prepared by the present invention under moving air component;
The scanning electron microscope (SEM) photograph of Fig. 4 silica-base material prepared by the present invention;
The transmission of Fig. 5 composite material prepared by the present invention and scanning transmission electron microscope figure;
The electrochemistry cycle performance figure of Fig. 6 electrode material prepared by the present invention;
Fig. 7 is the cyclic voltammogram of electrode material under 0.1mv sweeps speed prepared by the present invention.
Embodiment
Embodiment 1
Thiophene rate of charge is the preparation method of 30%: join in 150mL chloroform by 1.7505g nano silica fume and 5.7836g anhydrous ferric trichloride, electric stirring 30 minutes, and solution is dirty-green; Utilize peristaltic pump slowly to add in above-mentioned mixed liquor after 0.7509g thiophene is dissolved in 50mL chloroform also fully to stir, stir speed for 350r/min; Then in Oxidation at room temperature polymerization 10h; Reaction terminates rear suction filtration, with absolute ethanol washing 3 times, then uses the pickling of 1mol/L salt, then aobvious neutral to solution for several times with a large amount of deionized water washing, finally in 50 DEG C of vacuumize 10h, obtains composite material.
Claim 0.2810g composite material, 0.0795g conductive acetylene is black, and 0.0406g contracting sodium carboxymethylcellulose pyce, fully grinds, and mixed-powder being placed in small beaker, to add deionized water a little, after stirring 12h on Copper Foil smear.With 2025 button cell shells, barrier film is PP/PE/PP, with the LiPF of 1mol/L
6as electrolyte, solvent is dimethyl carbonate, ethylene carbonate, methyl ethyl carbonate (mol ratio 1:1:1) to add volume ratio be that the vinylene carbonate (CV) of 3% is as stabilizer, do electrode with lithium sheet, under argon shield, be assembled into button cell with glove box; The test of electrochemistry cycle performance is carried out under voltage range is 0.02 ~ 1.5V, 100mA/g current density.After carrying out 50 charge-discharge tests, specific capacity still maintains 501mAh/g.
Embodiment 2
Thiophene rate of charge is the preparation method of 20%: join in 150mL chloroform by 3.0002g nano silica fume and 5.7842g anhydrous ferric trichloride, electric stirring 30 minutes, and solution is dirty-green; Utilize peristaltic pump slowly to add in above-mentioned mixed liquor after 0.7513g thiophene is dissolved in 50mL chloroform also fully to stir, stir speed for 350r/min; Then Oxidation at room temperature polymerization 10h.Reaction terminates rear suction filtration, with absolute ethanol washing 3 times, then uses the pickling of 1mol/L salt, then aobvious neutral to solution for several times with a large amount of deionized water washing, finally at 50 DEG C of vacuumize 10h, obtains composite material.
Claim 0.2820g composite material, 0.0810g conductive acetylene is black, and 0.0410g contracting sodium carboxymethylcellulose pyce, fully grinds, and mixed-powder being placed in small beaker, to add deionized water a little, after stirring 12h on Copper Foil smear.With 2025 button cell shells, barrier film is PP/PE/PP, with the LiPF of 1mol/L
6as electrolyte; solvent is dimethyl carbonate, ethylene carbonate, methyl ethyl carbonate (mol ratio 1:1:1) to add volume ratio be that the vinylene carbonate (CV) of 3% is as stabilizer; do electrode with lithium sheet, under argon shield, be assembled into button cell with glove box.The test of electrochemistry cycle performance is carried out under voltage range is 0.02 ~ 1.5V, 100mA/g current density.Carry out 50 charge-discharge tests, specific capacity still maintains 375mAh/g.
Embodiment 3
Thiophene rate of charge is the preparation method of 40%: join in 150mL chloroform by 1.1258g nano silica fume and 5.7827g anhydrous ferric trichloride, and electric stirring 30 minutes makes solution be dirty-green; Utilize peristaltic pump slowly to add in above-mentioned mixed liquor after 0.7500g thiophene is dissolved in 50mL chloroform also fully to stir, stir speed for 350r/min; Then in Oxidation at room temperature polymerization 10h.Reaction terminates rear suction filtration, first uses absolute ethanol washing 3 times, with the pickling of 1mol/L salt, then aobvious neutral to solution for several times with a large amount of deionized water washing, finally in 50 DEG C of vacuumize 10h, obtains composite material.
Claim 0.2815g composite material, 0.0800g conductive acetylene is black, and 0.0399g contracting sodium carboxymethylcellulose pyce, fully grinds, and mixed-powder being placed in small beaker, to add deionized water a little, after stirring 12h on Copper Foil smear.With 2025 button cell shells, barrier film is PP/PE/PP, with the LiPF of 1mol/L
6as electrolyte; solvent is dimethyl carbonate, ethylene carbonate, methyl ethyl carbonate (mol ratio 1:1:1) to add volume ratio be that the vinylene carbonate (CV) of 3% is as stabilizer; do electrode with lithium sheet, under argon shield, be assembled into button cell with glove box.The test of electrochemistry cycle performance is carried out under voltage range is 0.02 ~ 1.5V, 100mA/g current density.After carrying out 50 charge-discharge tests, specific capacity still maintains 224mAh/g.
Claims (7)
1. for nano-silicon-polythiophene conductive composite material of lithium ion battery negative material, it is characterized in that: at the outer even coated one deck conductive polythiophene of silicon nanoparticle.
2. as claimed in claim 1 for the nano-silicon-polythiophene conductive composite material of lithium ion battery, it is characterized in that: the mass percent 7.5 ~ 34.2% of conductive polythiophene, the mass percent of silicon nanoparticle is 65.8 ~ 92.5%.
3. as claimed in claim 1 for the preparation method of the nano-silicon-polythiophene conductive composite material of lithium ion battery, be embedding lithium active material with nano silicon particles, thiophene is polymerization single polymerization monomer, chloroform is solvent, anhydrous ferric trichloride is oxidant, obtains nano-silicon-polythiophene composite material by in-situ polymerization.
4. as claimed in claim 3 for the preparation method of the nano-silicon-polythiophene conductive composite material of lithium ion battery, it is characterized in that: first nano silicon particles and oxidant ferric trichloride are scattered in chloroform, the polymerization single polymerization monomer thiophene dissolved with ethanol is added, in polymerized at room temperature reaction 3 ~ 20h under stirring after stirring; Reaction terminates rear suction filtration, and successively by absolute ethyl alcohol, hydrochloric acid, deionized water washing extremely neutrality, vacuumize, grinds and get final product.
5. as described in claim 3 or 4 for the preparation method of the nano-silicon of lithium ion battery-polythiophene conductive composite material, it is characterized in that: the mass ratio of nano silicon particles and thiophene monomer is 9:1 ~ 1:1.
6. as described in claim 3 or 4 for the preparation method of the nano-silicon polythiophene conductive composite material of lithium ion battery, it is characterized in that: the mol ratio of ferric trichloride and thiophene monomer is 2:1 ~ 6:1.
7. as described in claim 3 or 4 for the preparation method of the nano-silicon of lithium ion battery-polythiophene conductive composite material, it is characterized in that: the particle diameter of nano silicon particles is 20 ~ 160nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105958031A (en) * | 2016-06-30 | 2016-09-21 | 湖南桑顿新能源有限公司 | Sulfur-based cathode composite material and preparation method thereof |
| CN106654273A (en) * | 2017-02-06 | 2017-05-10 | 安徽鹰龙工业设计有限公司 | Organic cathode material for lithium battery, and preparation method thereof |
| CN110931727A (en) * | 2019-10-25 | 2020-03-27 | 合肥国轩高科动力能源有限公司 | Preparation method of conductive polymer-coated silicon-based negative electrode material |
| WO2021017944A1 (en) * | 2019-07-29 | 2021-02-04 | 宁德时代新能源科技股份有限公司 | Negative electrode active material, manufacturing method thereof, and secondary battery, battery module, battery pack and device relating thereto |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007018794A (en) * | 2005-07-06 | 2007-01-25 | Bridgestone Corp | Carbon material electrode, its manufacturing method and nonaqueous electrolyte secondary battery |
| CN101210119A (en) * | 2006-12-29 | 2008-07-02 | 比亚迪股份有限公司 | Silicon-containing composite material and its preparation method and application |
| CN101630728A (en) * | 2009-04-16 | 2010-01-20 | 华中科技大学 | High energy density lithium secondary battery electrode and preparation method thereof |
-
2014
- 2014-09-23 CN CN201410489470.9A patent/CN104393299B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007018794A (en) * | 2005-07-06 | 2007-01-25 | Bridgestone Corp | Carbon material electrode, its manufacturing method and nonaqueous electrolyte secondary battery |
| CN101210119A (en) * | 2006-12-29 | 2008-07-02 | 比亚迪股份有限公司 | Silicon-containing composite material and its preparation method and application |
| CN101630728A (en) * | 2009-04-16 | 2010-01-20 | 华中科技大学 | High energy density lithium secondary battery electrode and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李瑞荣等: "锂离子电池硅基负极材料的研究进展", 《材料导报A:综述篇》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105958031A (en) * | 2016-06-30 | 2016-09-21 | 湖南桑顿新能源有限公司 | Sulfur-based cathode composite material and preparation method thereof |
| CN106654273A (en) * | 2017-02-06 | 2017-05-10 | 安徽鹰龙工业设计有限公司 | Organic cathode material for lithium battery, and preparation method thereof |
| WO2021017944A1 (en) * | 2019-07-29 | 2021-02-04 | 宁德时代新能源科技股份有限公司 | Negative electrode active material, manufacturing method thereof, and secondary battery, battery module, battery pack and device relating thereto |
| US11695112B2 (en) | 2019-07-29 | 2023-07-04 | Contemporary Amperex Technology Co., Limited | Negative electrode active material, process for preparing the same, and secondary battery, battery module, battery pack and apparatus related to the same |
| CN110931727A (en) * | 2019-10-25 | 2020-03-27 | 合肥国轩高科动力能源有限公司 | Preparation method of conductive polymer-coated silicon-based negative electrode material |
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