CN104143629A - Method for preparing Si/C/graphite composite negative electrode material - Google Patents
Method for preparing Si/C/graphite composite negative electrode material Download PDFInfo
- Publication number
- CN104143629A CN104143629A CN201410383492.7A CN201410383492A CN104143629A CN 104143629 A CN104143629 A CN 104143629A CN 201410383492 A CN201410383492 A CN 201410383492A CN 104143629 A CN104143629 A CN 104143629A
- Authority
- CN
- China
- Prior art keywords
- mixture
- silicon
- graphite
- negative electrode
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/5835—Comprising fluorine or fluoride salts
-
- 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 method for preparing a Si/C/graphite composite negative electrode material. The method for preparing the Si/C/graphite composite negative electrode material comprises the following steps that micron silicon and an organic carbon source are evenly mixed, and deionized water or absolute ethyl alcohol is added to the mixture of the micron silicon and the organic carbon source; ball-milling is conducted on the obtained mixture, so that a nanometer silicon mixture which is evenly dispersed is obtained; a natural spherical graphite negative electrode material is obtained and is evenly mixed with the nanometer silicon mixture, deionized water or absolute ethyl alcohol is added to the mixture of the natural spherical graphite negative electrode material and the nanometer silicon mixture, and stirring is conducted; a mixture is obtained after drying, and a spherical particle precursor is obtained; under the nitrogen condition, the precursor is baked, cooled to the room temperature and then is crushed, and then the Si/C/graphite composite negative electrode material is obtained. According to the method for preparing the Si/C/graphite composite negative electrode material, the micron silicon is taken as the raw material, the Si/C/graphite composite negative electrode material high in cycle performance is prepared, the technology is simple and easy to control, and large-scale production of Si/C/graphite composite negative electrode materials can be achieved easily.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery silicon based composite material, particularly a kind of preparation method of Si/C/ graphite composite material.
Background technology
The advantages such as lithium ion battery has that energy density is large, voltage is high, has extended cycle life, memory-less effect, safety non-pollution, in medium extensive uses of portable type electronic product such as notebook computer, mobile phone, digital cameras, and become gradually the leading power supply of electric automobile and hybrid-electric car.Current commercial lithium ion battery negative material is Delanium and native graphite, but the theoretical capacity of graphite is only 372mAh/g, can not meet the demand of product to lithium ion battery high-energy-density.
Because silicon based anode material has high theoretical capacity, can reach 4200mAh/g, become the developing focus of high performance lithium ionic cell cathode material.But silicon based anode material will really be realized large-scale application in lithium ion battery, mainly also there is following problem: 1. Li
+repeatedly embed and deviate from and will cause distortion repeatedly and even the cracking of metal material inside, and then make electrode efflorescence lost efficacy; 2. in discharge process first, active material can form SEI film with electrolyte interface, consumes a part of lithium ion, the generation of irreversible lithium silicon alloy simultaneously, and efficiency is very low first to make electrode; 3. slow, the poorly conductive of lithium ion diffusive migration speed.For above-mentioned reasons, cause the cyclical stability of silicium cathode material very poor.
In order to solve the problem opposing between the high power capacity of silicon based anode material and cycle performance, in recent years, preparation has nanostructure or the compound electrode material of nanophase becomes the main path that improves silicon electrode ion kinetics of diffusion and cycle characteristics.
CN201310272353.2 discloses a kind of Si-C composite material that comprises shell carbon, between kernel Si-C composite material and shell carbon, comprises voided layer, can cushion the change in volume of silicon grain in charge and discharge process, improves the cycle performance of electrode.
CN201110161175.7 discloses that twice spraying of a kind of employing is dry, Si-C composite material method is prepared in once sintered processing, its concrete steps are: first silicon source, graphite and organic carbon source are scattered in and in solvent, form mixed liquor, dry the spherical nuclei material of spraying for the first time, then by dry to spherical nuclei material and the spraying of organic carbon source solution secondary, finally, by powder sintered gained processing, the material finally obtaining has the advantages such as specific capacity is high, multiplying power good cycling stability.
Said method complex process, the difficult control of condition, and nano-silicon cost is higher, is difficult to be applicable to large-scale production.
Summary of the invention
For the deficiency of prior art existence, the object of this invention is to provide a kind of preparation method of Si/C/ composite cathode material of silicon/carbon/graphite.Employing micron silicon is raw material, and preparation has better cycle performance Si/C/ composite cathode material of silicon/carbon/graphite, and technique of the present invention is simple, easy to control, is easily applicable to large-scale production.
The concrete technical scheme of the present invention:
1. the micron silicon of average grain diameter 1 ~ 5 μ m is evenly mixed by 1:1 ~ 10:1 mass ratio with organic carbon source, add deionized water or the absolute ethyl alcohol of 2 ~ 10 times of solid mixture weight;
2. by said mixture ball milling 2 ~ 6 hours, obtain homodisperse nano-silicon mixture;
3. get 0.5 ~ 2 times to step 1. average grain diameter 5 ~ 25 μ m natural spherical plumbago negative materials of solid mixture weight evenly mix with above-mentioned nano-silicon mixture, add deionized water or absolute ethyl alcohol, stir 0.5 ~ 2 hour;
4. inlet temperature is 200 ~ 350 DEG C, and outlet temperature is 90 ~ 150 DEG C, and the mixture that 3. spraying drying steps obtains, obtains spheric granules presoma;
5. under nitrogen atmosphere and 500 ~ 800 DEG C of conditions, the presoma roasting that 4. step is obtained 2 ~ 12 hours, is cooled to room temperature, and then fragmentation obtains Si/C/ graphite cathode material.
Organic carbon source of the present invention is glucose, sucrose or polyvinyl alcohol.
Coated model of the present invention as shown in Figure 1.At the coated one deck amorphous carbon in silicon nanoparticle surface, Si/C uniform particles is dispersed in the surface of spherical graphite particle, is a kind of Si/C/ composite cathode material of silicon/carbon/graphite with nucleocapsid structure.
The present invention adopts when once spraying is dry prepares micron ball forming core shell structure granules, taking the larger graphite of particle size as matrix, the mixture that nano-silicon and organic carbon source form is evenly dispersed in graphite granule around and forms suspension, this suspension contacts with the hot-air spraying into, solvent is volatilized rapidly, thereby obtain outer shell and contain silicon nanoparticle and organic carbon, the spherical or class spherical nucleocapsid pressed powder that kernel is graphite.Silicon nanoparticle had been finely dispersed mixture with organic carbon source before mixing with graphite, and in the time mixing with graphite, both still can be evenly dispersed in graphite granule surface.Spraying is dry is a kind of transient state drying means, after dry, the distribution of graphite surface silicon nanoparticle and organic carbon source is substantially similar to both distributions in above-mentioned suspension, only difference is organic carbon source curing molding after being dried, and silicon nanoparticle is embedded in organic carbon conductive matrices with disperse state.Therefore, the nucleocapsid structure material forming after sintering is mainly that nano-silicon disperse forms coating layer in RESEARCH OF PYROCARBON, and this coating layer is positioned at graphite granule surface.Because the dry front silicon grain of spraying is nano-scale, organic carbon source exists with molecular forms, and the size of graphite granule is relatively large, when three is dispersed in while carrying out atomization in solvent, tend to form the drop taking the relatively large graphite of sized particles as core, spherical nucleocapsid composite material of the present invention is easy to get.Spray drying technology has efficiency and balling ratio is high, can prevent nanoparticle agglomerates and simple operation and other advantages, is one of scale effective way of preparing spherical nucleocapsid particle.
Compared with prior art; the invention has the advantages that: a kind of silicon-carbon composite cathode material of lithium ion battery with clad structure of the present invention; under protective atmosphere, after heat treatment resulting materials structure is: taking graphite as kernel; silicon grain and agraphitic carbon serve as coating layer at graphite surface as a whole, and silicon grain is fixed in coating layer with the form of disperse and it is enclosed with agraphitic carbon around.Graphite and agraphitic carbon structural similarity, both can be preferably in junction, interface riveted mutually, the coating layer that makes to contain agraphitic carbon can depend on securely graphite matrix in charge and discharge process and silicon grain is fixed in coating layer network, so that whole coating layer does not come off.Agraphitic carbon and graphite in coating layer serves as " buffering skeleton " jointly, not only can be silicon generation volumetric expansion provides more spaces effectively to suppress electrode structure efflorescence inefficacy, and space in graphite and the agraphitic carbon conductive network and the structure that form can improve the conducting power of electronics and lithium ion, significantly improve material cyclical stability.
The present invention only once sprays to be dried and can obtain nucleocapsid Si-C composite material, efficiently simple, is easy to practical, prepared material and has the advantages such as reversible capacity is high, good cycle.
Brief description of the drawings
Fig. 1 is the coated model of Si/C/ graphite material of the present invention.
In figure: 1. graphite; 2.Si; 3. amorphous carbon.
Fig. 2 is Si/C/ composite cathode material of silicon/carbon/graphite XRD figure prepared by embodiment 1.
Fig. 3 is the first charge-discharge curve of the Si/C/ composite cathode material of silicon/carbon/graphite prepared of embodiment 1 under current density 100mA/g.
Fig. 4 is Si/C/ composite cathode material of silicon/carbon/graphite charge-discharge performance curve under current density 200mA/g prepared by embodiment 1.
Embodiment
Embodiment 1
The micron silica flour 100g that takes average grain diameter 1.5 μ m, glucose 50g evenly mixes, and then adds deionized water 500mL, and mixture, high energy ball mill ball milling 3 hours, is obtained to homodisperse nano-silicon mixture.
The natural spherical plumbago negative material that is 12 μ m by said mixture and 100g average grain diameter evenly mixes, and adds deionized water 500mL, stirs 0.5 hour; The dry inlet temperature of adjustable spraying is 300 DEG C, and outlet temperature is 120 DEG C, spray-dried, obtains spheric granules presoma; Under nitrogen atmosphere and 600 DEG C of conditions, by presoma roasting 6 hours, be cooled to room temperature, then fragmentation obtains Si/C/ graphite cathode material.
80:10:4:6 is taking deionized water as solvent in mass ratio for Si/C/ graphite cathode material, conductive black and the CMC that employing embodiment 1 makes and SBR binding agent, and rapid stirring forms slurry.Slurry is evenly coated on the 20 Cu paper tinsel disks that μ m is thick, diameter is 12mm and makes wet electrode, then wet electrode is placed at 60 DEG C and is dried, wait be dried to half-dried after, use tablet press machine electrode compacting, vacuumize 12h at 80 DEG C, makes work electrode subsequently.In the vacuum glove box that is full of argon gas by the EC+DEC+EMC(volume ratio 1:1:1 of work electrode, metal lithium sheet, Celgard2400 barrier film, 1mol/L LiPF6) electrolyte is assembled into 2032 type button cells, button cell carries out electric performance test after leaving standstill 24 hours, and voltage range is 0.01V ~ 1.5V.Test result as shown in Figure 4 and Table 1.
As shown in Figure 4 and Table 1, adopt the material of embodiment 1 to make experiment button cell, specific capacity reaches 553.1mAh/g, and first charge-discharge efficiency is 80.4%, and the capacity attenuation rate after 50 times that circulates is only 3.7%, has excellent cyclical stability.
Embodiment 2
The micron silica flour 100g that takes average grain diameter 5 μ m, sucrose 80g evenly mixes, and then adds deionized water 1000mL, and mixture, high energy ball mill ball milling 6 hours, is obtained to homodisperse nano-silicon mixture.
The natural spherical plumbago negative material that is 20 μ m by said mixture and 120g average grain diameter evenly mixes, and adds absolute ethyl alcohol 200mL, stirs 2 hours; The dry inlet temperature of adjustable spraying is 250 DEG C, and outlet temperature is 100 DEG C, spray-dried, obtains spheric granules presoma; Under nitrogen atmosphere and 800 DEG C of conditions, by presoma roasting 8 hours, be cooled to room temperature, then fragmentation obtains Si/C/ graphite cathode material.
Make experiment button cell by the method identical with embodiment 1.
Experiment button cell as shown in table 1, the material of embodiment 2 is made, specific capacity reaches 627.7mAh/g, and first charge-discharge efficiency is 74.1%, and but circulate, after 50 times, capacity attenuation rate is up to 12.5%, and cycle performance is very poor.
Embodiment 3
The micron silica flour 100g that takes average grain diameter 1 μ m, polyvinyl alcohol 10g evenly mixes, and then adds absolute ethyl alcohol 500mL, and mixture, high energy ball mill ball milling 2 hours, is obtained to homodisperse nano-silicon mixture.
The natural spherical plumbago negative material that is 25 μ m by said mixture and 100g average grain diameter evenly mixes, and adds absolute ethyl alcohol 500mL, stirs 2 hours; The dry inlet temperature of adjustable spraying is 350 DEG C, and outlet temperature is 150 DEG C, spray-dried, obtains spheric granules presoma; Under nitrogen atmosphere and 800 DEG C of conditions, by presoma roasting 4 hours, be cooled to room temperature, then fragmentation obtains Si/C/ graphite cathode material.
Make experiment button cell by the method identical with embodiment 1.
Experiment button cell as shown in table 1, the material of embodiment 3 is made, specific capacity reaches 508.5mAh/g, and first charge-discharge efficiency is 75.7%, and the capacity attenuation rate after 50 times that circulates is 7.4%, and cycle performance is poor.
Embodiment 4
The micron silica flour 100g that takes average grain diameter 3 μ m, glucose 100g evenly mixes, and then adds deionized water 800mL, and mixture, high energy ball mill ball milling 5 hours, is obtained to homodisperse nano-silicon mixture.
The natural spherical plumbago negative material that is 15 μ m by said mixture and 150g average grain diameter evenly mixes, and adds deionized water 500mL, stirs 1 hour; The dry inlet temperature of adjustable spraying is 300 DEG C, and outlet temperature is 120 DEG C, spray-dried, obtains spheric granules presoma; Under nitrogen atmosphere and 600 DEG C of conditions, by presoma roasting 3 hours, be cooled to room temperature, then fragmentation obtains Si/C/ graphite cathode material.
Make experiment button cell by the method identical with embodiment 1.
Experiment button cell as shown in table 1, the material of embodiment 4 is made, specific capacity reaches 516.8mAh/g, and first charge-discharge efficiency is 76.0%, and the capacity attenuation rate after 50 times that circulates is 6.8%, and cycle performance is better.
Embodiment 5
The micron silica flour 100g that takes average grain diameter 2 μ m, sucrose 30g evenly mixes, and then adds deionized water 400mL, and mixture, high energy ball mill ball milling 5 hours, is obtained to homodisperse nano-silicon mixture.
The natural spherical plumbago negative material that is 18 μ m by said mixture and 80g average grain diameter evenly mixes, and adds deionized water 500mL, stirs 1 hour; The dry inlet temperature of adjustable spraying is 300 DEG C, and outlet temperature is 120 DEG C, spray-dried, obtains spheric granules presoma; Under nitrogen atmosphere and 500 DEG C of conditions, by presoma roasting 3 hours, be cooled to room temperature, then fragmentation obtains Si/C/ graphite cathode material.
Make experiment button cell by the method identical with embodiment 1.
Experiment button cell as shown in table 1, the material of embodiment 5 is made, specific capacity reaches 490.6mAh/g, first charge-discharge efficiency is 73.5%, circulate 50 times afterwards capacity attenuation rate be 9.3%, not only capacity and efficiency is low first, cycle performance is also poor.
Embodiment 6
The micron silica flour 100g that takes average grain diameter 1 μ m, polyvinyl alcohol 30g evenly mixes, and then adds absolute ethyl alcohol 600mL, and mixture, high energy ball mill ball milling 4 hours, is obtained to homodisperse nano-silicon mixture.
The natural spherical plumbago negative material that is 10 μ m by said mixture and 150g average grain diameter evenly mixes, and adds absolute ethyl alcohol 600mL, stirs 2 hours; The dry inlet temperature of adjustable spraying is 350 DEG C, and outlet temperature is 150 DEG C, spray-dried, obtains spheric granules presoma; Under nitrogen atmosphere and 800 DEG C of conditions, by presoma roasting 6 hours, be cooled to room temperature, then fragmentation obtains Si/C/ graphite cathode material.
Make experiment button cell by the method identical with embodiment 1.
Experiment button cell as shown in table 1, the material of embodiment 6 is made, specific capacity reaches 542.3mAh/g, and first charge-discharge efficiency is 78.3%, and the capacity attenuation rate after 50 times that circulates is 5.1%, and cycle performance is better.
Embodiment 1 ~ 6 discharges and recharges and carries out electrochemical property test with 200mA/g electric current, and result is as shown in table 1.
Table 1 Si/C/ graphite cathode material chemical property
Can find out from the result of table 1, the Si/C/ graphite cathode material that adopts the present invention to prepare has good chemical property.Wherein, Si/C/ graphite cathode material chemical property prepared by embodiment 1 is better, can find out from the XRD figure of Fig. 2, and material is mainly made up of silicon and graphite-phase.Discharge and recharge with 200mA/g electric current, its specific discharge capacity can reach 553.1mAh/g, and first charge-discharge efficiency is 80.4%, and after 50 circulations, its special capacity fade rate is only 3.7%.
Claims (2)
1. a Si/C/ composite cathode material of silicon/carbon/graphite preparation method, is characterized in that step is as follows:
1. the micron silicon of average grain diameter 1 ~ 5 μ m is evenly mixed by 1:1 ~ 10:1 mass ratio with organic carbon source, add deionized water or the absolute ethyl alcohol of 2 ~ 10 times of solid mixture weight;
2. by said mixture ball milling 2 ~ 6 hours, obtain homodisperse nano-silicon mixture;
3. get 0.5 ~ 2 times to step 1. average grain diameter 5 ~ 25 μ m natural spherical plumbago negative materials of solid mixture weight evenly mix with above-mentioned nano-silicon mixture, add deionized water or absolute ethyl alcohol, stir 0.5 ~ 2 hour;
4. inlet temperature is 200 ~ 350 DEG C, and outlet temperature is 90 ~ 150 DEG C, and the mixture that 3. spraying drying steps obtains, obtains spheric granules presoma;
5. under nitrogen atmosphere and 500 ~ 800 DEG C of conditions, the presoma roasting that 4. step is obtained 2 ~ 12 hours, is cooled to room temperature, and then fragmentation obtains Si/C/ graphite cathode material.
2. Si/C/ composite cathode material of silicon/carbon/graphite preparation method according to claim 1, is characterized in that described organic carbon source is glucose, sucrose or polyvinyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410383492.7A CN104143629A (en) | 2014-08-06 | 2014-08-06 | Method for preparing Si/C/graphite composite negative electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410383492.7A CN104143629A (en) | 2014-08-06 | 2014-08-06 | Method for preparing Si/C/graphite composite negative electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104143629A true CN104143629A (en) | 2014-11-12 |
Family
ID=51852757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410383492.7A Pending CN104143629A (en) | 2014-08-06 | 2014-08-06 | Method for preparing Si/C/graphite composite negative electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104143629A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489855A (en) * | 2015-11-25 | 2016-04-13 | 天津师范大学 | Core-shell silicon carbon composite negative electrode material for high-capacity type lithium ion battery and preparation method therefor |
| CN105489871A (en) * | 2015-12-29 | 2016-04-13 | 国联汽车动力电池研究院有限责任公司 | Silicon, silicon-oxygen-carbon and graphene-based composite material, and preparation method and application thereof |
| CN105609730A (en) * | 2016-01-05 | 2016-05-25 | 广州有色金属研究院 | Preparation method for silicon/carbon/graphite composite negative electrode material |
| CN106025221A (en) * | 2016-06-24 | 2016-10-12 | 广东省稀有金属研究所 | Preparation method for silicon/carbon/graphite composite negative electrode material |
| CN107275571A (en) * | 2017-08-18 | 2017-10-20 | 华南师范大学 | A kind of full battery of lithium sulfide/nano-silicone wire/carbon and preparation method and application |
| CN108346788A (en) * | 2018-01-31 | 2018-07-31 | 广东省稀有金属研究所 | A kind of preparation method of carbon coating Antaciron composite negative pole material |
| CN108682829A (en) * | 2018-06-11 | 2018-10-19 | 清华大学深圳研究生院 | A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material |
| CN108899522A (en) * | 2018-07-06 | 2018-11-27 | 湖北工程学院 | A kind of high-volume silicon-carbon negative electrode material, preparation method and application |
| CN109565036A (en) * | 2018-09-28 | 2019-04-02 | 香港应用科技研究院有限公司 | Active material of positive electrode for lithium ion battery |
| CN109786670A (en) * | 2019-01-24 | 2019-05-21 | 南开大学 | A kind of preparation method of the negative electrode of lithium ionic secondary battery of Gao Shouxiao |
| CN109980206A (en) * | 2019-04-02 | 2019-07-05 | 溧阳紫宸新材料科技有限公司 | Preparation method, negative electrode material and the lithium ion battery of low bulk silicon-carbon cathode material |
| CN110600684A (en) * | 2018-09-12 | 2019-12-20 | 湖北万润新能源科技发展有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN110902667A (en) * | 2019-12-04 | 2020-03-24 | 绍兴文理学院 | Preparation method of porous Si/C negative electrode material |
| WO2020062354A1 (en) * | 2018-09-28 | 2020-04-02 | Hong Kong Applied Science and Technology Research Institute Company Limited | Anode Active Materials for Lithium-ion Batteries |
| CN111180712A (en) * | 2020-01-22 | 2020-05-19 | 佛山科学技术学院 | Nano silicon/carbon nano tube microsphere/graphite composite structure negative electrode material and preparation method thereof |
| CN112652739A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN114361426A (en) * | 2022-01-25 | 2022-04-15 | 山西大学 | Preparation method and application of biomass-based silicon-carbon composite material |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030096168A1 (en) * | 2000-03-07 | 2003-05-22 | Shinji Kasamatsu | Non-aqueous electrolyte secondary battery |
| CN101286560A (en) * | 2008-05-30 | 2008-10-15 | 成都中科来方能源科技有限公司 | Composite cathode material for lithium ion cell and preparing method thereof |
| CN101979317A (en) * | 2010-10-09 | 2011-02-23 | 武汉理工大学 | Low-temperature ball milling preparation method for nano crystal silicon powder |
| CN102244240A (en) * | 2011-06-15 | 2011-11-16 | 中南大学 | Lithium ion battery composite anode material and preparation method thereof |
| CN102544445A (en) * | 2010-12-29 | 2012-07-04 | 海洋王照明科技股份有限公司 | Preparation method for graphene composite material supporting silicon nanoparticles |
| CN102891297A (en) * | 2012-11-10 | 2013-01-23 | 江西正拓新能源科技有限公司 | Silicon-carbon composite material for lithium ion battery and preparation method thereof |
| CN103022448A (en) * | 2012-12-19 | 2013-04-03 | 天津巴莫科技股份有限公司 | Method for preparing lithium battery silicon carbon anode material |
| CN103346305A (en) * | 2013-07-01 | 2013-10-09 | 华南师范大学 | Preparation and application of lithium battery silicon-carbon composite material taking synthetic graphite as carrier |
| CN203333311U (en) * | 2013-05-23 | 2013-12-11 | 苏州金瑞晨科技有限公司 | Plasma device for preparing nanometer silicon powder |
| CN103474667A (en) * | 2013-08-16 | 2013-12-25 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof |
| CN103560234A (en) * | 2013-11-14 | 2014-02-05 | 南京毕汉特威高分子材料有限公司 | Composite graphite-silicon lithium ion battery cathode material and preparation method thereof |
| CN103633295A (en) * | 2012-08-23 | 2014-03-12 | 上海杉杉科技有限公司 | Silicon-carbon composite material, lithium ion battery, and preparation method and application of silicon-carbon composite material |
-
2014
- 2014-08-06 CN CN201410383492.7A patent/CN104143629A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030096168A1 (en) * | 2000-03-07 | 2003-05-22 | Shinji Kasamatsu | Non-aqueous electrolyte secondary battery |
| CN101286560A (en) * | 2008-05-30 | 2008-10-15 | 成都中科来方能源科技有限公司 | Composite cathode material for lithium ion cell and preparing method thereof |
| CN101979317A (en) * | 2010-10-09 | 2011-02-23 | 武汉理工大学 | Low-temperature ball milling preparation method for nano crystal silicon powder |
| CN102544445A (en) * | 2010-12-29 | 2012-07-04 | 海洋王照明科技股份有限公司 | Preparation method for graphene composite material supporting silicon nanoparticles |
| CN102244240A (en) * | 2011-06-15 | 2011-11-16 | 中南大学 | Lithium ion battery composite anode material and preparation method thereof |
| CN103633295A (en) * | 2012-08-23 | 2014-03-12 | 上海杉杉科技有限公司 | Silicon-carbon composite material, lithium ion battery, and preparation method and application of silicon-carbon composite material |
| CN102891297A (en) * | 2012-11-10 | 2013-01-23 | 江西正拓新能源科技有限公司 | Silicon-carbon composite material for lithium ion battery and preparation method thereof |
| CN103022448A (en) * | 2012-12-19 | 2013-04-03 | 天津巴莫科技股份有限公司 | Method for preparing lithium battery silicon carbon anode material |
| CN203333311U (en) * | 2013-05-23 | 2013-12-11 | 苏州金瑞晨科技有限公司 | Plasma device for preparing nanometer silicon powder |
| CN103346305A (en) * | 2013-07-01 | 2013-10-09 | 华南师范大学 | Preparation and application of lithium battery silicon-carbon composite material taking synthetic graphite as carrier |
| CN103474667A (en) * | 2013-08-16 | 2013-12-25 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof |
| CN103560234A (en) * | 2013-11-14 | 2014-02-05 | 南京毕汉特威高分子材料有限公司 | Composite graphite-silicon lithium ion battery cathode material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 唐宗薰: "《普通高等教育"十五"国家级规划教材中级无机化学》", 31 December 2003 * |
| 李敏: "以石墨为母体的硅碳核壳复合负极材料的制备及性能研究", 《功能材料》 * |
| 王保峰: "球形硅/碳复合材料的制备及其电化学性能", 《第十二届中国固态离子学学术会议论文集稀土专辑》 * |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489855A (en) * | 2015-11-25 | 2016-04-13 | 天津师范大学 | Core-shell silicon carbon composite negative electrode material for high-capacity type lithium ion battery and preparation method therefor |
| CN105489855B (en) * | 2015-11-25 | 2017-11-14 | 天津师范大学 | High capacity type lithium ion battery nucleocapsid silicon-carbon composite cathode material and preparation method thereof |
| CN105489871A (en) * | 2015-12-29 | 2016-04-13 | 国联汽车动力电池研究院有限责任公司 | Silicon, silicon-oxygen-carbon and graphene-based composite material, and preparation method and application thereof |
| CN105609730A (en) * | 2016-01-05 | 2016-05-25 | 广州有色金属研究院 | Preparation method for silicon/carbon/graphite composite negative electrode material |
| CN105609730B (en) * | 2016-01-05 | 2018-06-01 | 广东省稀有金属研究所 | A kind of preparation method of silicon/carbon graphite composite negative pole material |
| CN106025221B (en) * | 2016-06-24 | 2018-12-07 | 广东省稀有金属研究所 | A kind of preparation method of silicon/carbon graphite composite negative pole material |
| CN106025221A (en) * | 2016-06-24 | 2016-10-12 | 广东省稀有金属研究所 | Preparation method for silicon/carbon/graphite composite negative electrode material |
| CN107275571A (en) * | 2017-08-18 | 2017-10-20 | 华南师范大学 | A kind of full battery of lithium sulfide/nano-silicone wire/carbon and preparation method and application |
| CN108346788A (en) * | 2018-01-31 | 2018-07-31 | 广东省稀有金属研究所 | A kind of preparation method of carbon coating Antaciron composite negative pole material |
| CN108346788B (en) * | 2018-01-31 | 2021-01-15 | 广东省稀有金属研究所 | Preparation method of carbon-coated ferrosilicon composite negative electrode material |
| CN108682829A (en) * | 2018-06-11 | 2018-10-19 | 清华大学深圳研究生院 | A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material |
| CN108682829B (en) * | 2018-06-11 | 2020-10-23 | 清华大学深圳研究生院 | Preparation method of nitrogen-doped carbon-coated silicon composite graphite material |
| CN108899522A (en) * | 2018-07-06 | 2018-11-27 | 湖北工程学院 | A kind of high-volume silicon-carbon negative electrode material, preparation method and application |
| CN108899522B (en) * | 2018-07-06 | 2020-06-12 | 湖北工程学院 | High-capacity silicon-carbon negative electrode material, preparation method and application |
| CN110600684A (en) * | 2018-09-12 | 2019-12-20 | 湖北万润新能源科技发展有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN109565036A (en) * | 2018-09-28 | 2019-04-02 | 香港应用科技研究院有限公司 | Active material of positive electrode for lithium ion battery |
| WO2020062354A1 (en) * | 2018-09-28 | 2020-04-02 | Hong Kong Applied Science and Technology Research Institute Company Limited | Anode Active Materials for Lithium-ion Batteries |
| US20200106124A1 (en) * | 2018-09-28 | 2020-04-02 | Hong Kong Applied Science and Technology Research Institute Company Limited | Anode Active Materials for Lithium-ion Batteries |
| CN109786670A (en) * | 2019-01-24 | 2019-05-21 | 南开大学 | A kind of preparation method of the negative electrode of lithium ionic secondary battery of Gao Shouxiao |
| CN109786670B (en) * | 2019-01-24 | 2021-08-06 | 南开大学 | Preparation method of high-first-efficiency lithium ion secondary battery negative electrode active material |
| CN109980206A (en) * | 2019-04-02 | 2019-07-05 | 溧阳紫宸新材料科技有限公司 | Preparation method, negative electrode material and the lithium ion battery of low bulk silicon-carbon cathode material |
| CN112652739A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN110902667A (en) * | 2019-12-04 | 2020-03-24 | 绍兴文理学院 | Preparation method of porous Si/C negative electrode material |
| CN111180712A (en) * | 2020-01-22 | 2020-05-19 | 佛山科学技术学院 | Nano silicon/carbon nano tube microsphere/graphite composite structure negative electrode material and preparation method thereof |
| CN114361426A (en) * | 2022-01-25 | 2022-04-15 | 山西大学 | Preparation method and application of biomass-based silicon-carbon composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104143629A (en) | Method for preparing Si/C/graphite composite negative electrode material | |
| CN102376944B (en) | Method for preparing silicon carbide alloy negative electrode material for lithium ion battery | |
| CN106784707B (en) | A kind of preparation method of nano-silicon-carbon composition lithium ion battery cathode material | |
| CN106784640B (en) | Silicon-based composite negative electrode material for lithium ion battery, preparation method of silicon-based composite negative electrode material and lithium ion battery negative electrode containing silicon-based composite negative electrode material | |
| CN103311515B (en) | A kind of graphene-based silicon-carbon composite cathode material and preparation method thereof | |
| CN106711461A (en) | Spherical porous silicon/carbon composite material as well as preparation method and application thereof | |
| CN106299314B (en) | A kind of lithium ion battery negative material and preparation method thereof, lithium ion battery | |
| CN101969111B (en) | Silicon-carbon alloy cathode material for lithium ion batteries and preparation method thereof | |
| CN105731427B (en) | A kind of graphite negative material of lithium ion battery and preparation method thereof | |
| CN106025222A (en) | Preparation method for coated silicon/carbon/graphite composite negative electrode material | |
| CN106784714A (en) | A kind of silicon-based composite anode material for Li-ion battery and preparation method thereof | |
| CN103682327B (en) | Based on the lithium ion battery and preparation method thereof of the hollow porous nickel oxide composite material of N doping carbon-coating parcel | |
| CN104752696A (en) | Preparation method of graphene-based silicon and carbon composite negative electrode material | |
| CN103259005B (en) | A kind of preparation method of high power capacity high rate lithium ionic cell cathode material | |
| CN101800304B (en) | Different-orientation spherical natural graphite negative electrode material and preparation method thereof | |
| CN102651476A (en) | Lithium ion battery silicon carbide composite anode material and preparation method thereof | |
| CN103311514B (en) | A kind of preparation method of modification lithium-ion battery graphite cathode material | |
| CN102394288A (en) | Silicon-carbon cathode material for lithium ion battery and manufacturing method thereof | |
| CN101859886A (en) | Lithium ion battery anode material and preparation method thereof | |
| CN105932284B (en) | A kind of close cladded type composite material and preparation method of mesoporous carbon and application | |
| CN108598391A (en) | A kind of nano silicon composite cathode material for lithium ion battery | |
| CN104966828A (en) | Preparation method of high-capacity lithium battery negative electrode material | |
| CN103326009B (en) | A kind of preparation method of high capacity lithium titanate anode material | |
| CN102299330A (en) | Active carbon-nano silicon composite powder, synthetic method thereof and lithium ion battery prepared therefrom | |
| CN106207177A (en) | Containing artificial SEI floor height volume and capacity ratio and the silicon-carbon cathode material of cycle performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141112 |
|
| WD01 | Invention patent application deemed withdrawn after publication |