CN111081981A - Preparation method of self-supporting double-sided silicon-graphene composite cathode - Google Patents
Preparation method of self-supporting double-sided silicon-graphene composite cathode Download PDFInfo
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- 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
- 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
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- H—ELECTRICITY
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- 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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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
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Abstract
The invention belongs to the technical field of chemical power supplies, and relates to a preparation method of a self-supporting double-sided silicon-graphene composite cathode. S1, mixing a graphene material, a conductive agent and a binder in proportion, adding an organic solvent to prepare a precursor solution, and preparing a self-supporting graphene electrode plate in a membrane rolling manner; s2, placing the graphene electrode plate in a vacuum oven; s3, placing the self-supporting graphene electrode plate on a sample rack in PECVD equipment, and vacuumizing to 8 x 10‑4Pa; s4, introducing silane and hydrogen into equipment, and doping silicon by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method; s5, repeating S3 and S on the reverse side of the self-supporting graphene electrode sheetS4, obtaining the double-sided self-supporting silicon-graphene negative plate, which not only can reduce the number of unstable functional groups on the surface of graphene and the change of silicon volume, but also improves the first effect and cycle performance of the silicon negative electrode.
Description
Technical Field
The invention belongs to the technical field of chemical power supplies, and relates to a preparation method of a self-supporting double-sided silicon-graphene composite cathode.
Background
With the rapid development of the information era and the increasingly serious environmental problems caused by air pollution, the great demand and wide application of portable electronic equipment and electric vehicles become increasingly urgent, and the demand of lithium ion batteries with rapid charge and discharge, high specific energy and long cycle life is urgent. The negative electrode material of the lithium ion battery applied to the market at present is mainly a carbon material, however, the theoretical capacity of the carbon material is only 372mAh/g, and the carbon material is not suitable for the wide demand of the high-capacity high-power lithium ion battery.
In order to develop a high-capacity lithium ion battery, researchers search for a high-capacity novel negative electrode material capable of replacing a carbon material, wherein the silicon material has excellent theoretical storage capacity (4200mAh/g) and lower lithium intercalation potential (less than 0.5V) which are relatively satisfactory, and the content of silicon in the earth is extremely rich. However, the first coulombic efficiency and poor cycle performance of silicon materials limit their commercial applications. A large number of researches show that the silicon material as the lithium ion battery cathode material mainly has 4 defects: 1) the silicon material has huge volume change in the charging and discharging process, so that the electrode material is peeled off and collapsed; 2) the silicon material is irreversibly transformed from a crystalline state to a disordered state in the process of lithium intercalation and deintercalation, so that the material structure is damaged; 3) the silicon material has poor conductivity, the non-uniform reaction with lithium is reduced, and the cycle performance of the silicon material is reduced; 4) the smaller the silicon particles, the larger the specific surface area, the easier it is to discharge high capacity, but the nano-scale silicon particles are easily agglomerated, resulting in a decrease in electrochemical performance. There are also some disadvantages to graphene materials as battery negative electrodes, including: 1) the prepared single-layer graphene sheet layer is easy to accumulate, and the reduction of the specific surface area causes the graphene sheet layer to lose part of high lithium storage space; 2) the first coulombic efficiency was low, generally below 70%. Due to the large specific surface area and rich functional groups, electrolyte can be decomposed on the surface of graphene in the circulation process to form an SEI film; meanwhile, the residual oxygen-containing groups on the surface of the carbon material and lithium ions generate irreversible side reaction, so that the reversible capacity is further reduced; 3) the initial capacity decays quickly. Therefore, a large number of researches show that the silicon material and the graphene material cannot be used as the anode material alone.
In order to solve the above-mentioned problems and to exert the best performance of the two materials, many researchers have focused on preparing a composite negative electrode material of graphene and silicon materials, and there are generally 2 types of methods. The first category is mainly composites of silicon and carbon materials; the second category is mainly the design of silicon composites of different structures.
The existing method for solving the problems has the problems of high cost, complex process, difficult batch production and the like, and cannot well improve the first coulombic efficiency and the cycle performance of the silicon material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a self-supporting double-sided silicon-graphene composite negative electrode. According to the invention, silicon-containing plasmas (SiHx, x is 0-4) with different activities are formed by a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, and react with self-supporting graphene electrode plates and graphene functional groups to form a double-sided silicon-graphene composite cathode with a silicon-carbon structure, so that the number of unstable functional groups on the surface of graphene and the change of silicon volume are reduced, and the first efficiency and the cycle performance of the silicon cathode are improved.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
the invention discloses a preparation method of a self-supporting double-sided silicon-graphene composite cathode, which comprises the following steps:
s1, mixing the graphene material, the conductive agent and the binder in proportion, adding an organic solvent, stirring or ball-milling to form a precursor solution, and preparing a self-supporting graphene electrode plate in a membrane rolling manner;
s2, placing the self-supporting graphene electrode plate in a vacuum oven at the temperature of 100 ℃ and 150 ℃, and keeping for 12-24 h;
s3, placing the self-supporting graphene electrode plate on a sample rack in PECVD equipment, and vacuumizing to 8 x 10-4Pa；
S4, introducing silane and hydrogen into equipment, setting power to glow, decomposing silane gas and the like, bombarding a graphene electrode plate by utilizing silane plasma generated by glow, and doping silicon by utilizing a Plasma Enhanced Chemical Vapor Deposition (PECVD) method;
s5, reversely placing the self-supporting graphene electrode plate on the sample holder, and repeating the steps S3 and S4 to obtain the double-sided self-supporting silicon-graphene negative electrode plate.
In the above technical solution, preferably, the step of preparing the self-supporting graphene electrode sheet in S1 includes: mixing a g of graphene raw material and b g of conductive agent, adding c ml of alcohol, stirring for 3 hours at normal temperature to uniformly mix, adding d ml of binder, and stirring for 1 hour until the mixture is uniformly dispersed to form a dough-like colloid; rolling a graphene electrode plate with the thickness of about 100-200 microns by a membrane rolling method; wherein a: b: c: d is 1:0.1:10: 2.
In the above technical solution, it is further preferable that the step S4 includes: setting the starting power to be 80-100W, introducing 10sccm silane and 30sccm hydrogen, and performing glow sputtering for 5-15min to prepare the self-supporting silicon-graphene composite cathode.
In the above technical solution, it is further preferable that the graphene material is one or a combination of graphene prepared from artificial graphite or natural graphite and graphene oxide.
In the above technical solution, it is further preferable that the conductive agent is one or a combination of more of acetylene black, Super P, Super S, 350G, carbon fiber, carbon nanotube, ketjen black, graphite conductive agent, and graphene.
In the above technical solution, it is further preferable that the binder is an aqueous or oily binder, and includes one or a combination of more of polytetrafluoroethylene, polyvinylidene fluoride, polyethylene oxide, polypropylene carbonate, polyethylene carbonate, polytrimethylene carbonate, polyvinyl alcohol, sodium carboxymethylcellulose, polyethylene, polypropylene and copolymers thereof, modified SBR, fluorinated rubber, and polyurethane.
In the above technical solution, it is further preferable that the organic solvent is one or a combination of more of N-methyl-2-pyrrolidone, alcohol, tetrahydrofuran, propylene carbonate, dimethyl (ethyl) carbonate, ethyl methyl carbonate, ethyl acetate, acetonitrile, isopropyl ether, acetone, butanone, isopropanol, butanol, hexane, cyclohexane, N-dimethylacetamide, benzene, toluene, dimethyl sulfoxide, carbon tetrachloride, trichloroethylene, and acetone.
The invention has the advantages and positive effects that:
according to the invention, silicon-containing plasmas (SiHx, x is 0-4) with different activities are formed by a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, and react with defects or functional groups at the edge of graphene through a macroporous structure of the graphene to form the double-sided silicon-graphene composite cathode with a silicon-carbon structure, so that the number of unstable functional groups on the surface of the graphene and the change of the volume of silicon are reduced, and the first efficiency and the cycle performance of the silicon cathode are improved. The following advantages are also provided:
1. the graphene electrode plate is of a self-supporting structure, does not have a current collector and is light in weight;
2. the graphene can greatly improve the conductivity of the silicon material;
3. the double-sided silicon-graphene composite negative electrode relieves the volume effect of silicon in the charging and discharging processes;
4. the preparation method of the self-supporting double-sided silicon-graphene composite negative electrode has the characteristics of easiness in preparation and large-scale production, and is an advantage candidate for preparing negative electrode plates with excellent performance in batches in the future;
5. the prepared double-sided self-supporting silicon-graphene composite negative electrode is beneficial to rapid charge and discharge, reduces the first irreversible capacity and improves the cycling stability of the material.
Drawings
Fig. 1 is a schematic view of a self-supporting silicon-graphene composite anode of a PECVD apparatus used in embodiment 1 of the present invention;
fig. 2 is a first charge-discharge diagram of a self-supporting graphene negative electrode in example 1 of the present invention;
fig. 3 is a first charge-discharge diagram of the self-supporting double-sided silicon-graphene composite negative electrode in example 1 of the present invention;
fig. 4 is a graph of the cycle performance of the self-supporting graphene negative electrode in example 1 of the present invention;
fig. 5 is a cycle performance diagram of the self-supporting graphene composite negative electrode and the double-sided silicon-graphene composite negative electrode in example 1 of the present invention.
Detailed Description
For a further understanding of the contents, features and effects of the present invention, the following examples are illustrated in the accompanying drawings and described in the following detailed description:
reference is made to figures 1, 2, 3, 4 and 5.
Example 1
A preparation method of a self-supporting double-sided silicon-graphene composite cathode is characterized in that the self-supporting double-sided silicon-graphene composite cathode, a lithium ion battery electrolyte and a cathode are assembled to form a lithium ion battery. The preparation process comprises the following steps:
step one, mixing 1g of graphene raw material with 0.1g of conductive agent (SP), adding 10ml of alcohol, stirring for 3 hours at normal temperature to uniformly mix the graphene raw material and the SP, adding 2ml of polytetrafluoroethylene binder, and stirring for 1 hour until the mixture is uniformly dispersed to form colloid similar to dough; rolling a graphene electrode plate with the thickness of about 100-200 microns by a membrane rolling method;
step two, cutting the electrode into electrode slices of 10cm multiplied by 10cm, and drying for 12 hours at the vacuum temperature of 100 ℃;
placing the electrode slice on a sample frame of PECVD equipment, adjusting the distance between substrates to be 10cm, vacuumizing to 8 x 10-4Pa, setting the power to be 80W, introducing 10sccm silane and 30sccm hydrogen, and performing glow sputtering for 5min to prepare a self-supporting silicon-graphene composite cathode;
and step four, reversely placing the sample on a sample rack, and repeating glow sputtering to obtain the self-supporting double-sided silicon-graphene composite negative plate.
Example 2
A preparation method of a self-supporting double-sided silicon-graphene composite cathode is characterized in that the self-supporting double-sided silicon-graphene composite cathode, a lithium ion battery electrolyte and a cathode are assembled to form a lithium ion battery. The preparation process comprises the following steps:
step one, mixing 1g of graphene raw material with 0.1g of conductive agent (SP), adding 10ml of alcohol, stirring for 3 hours at normal temperature to uniformly mix the graphene raw material and the SP, adding 2ml of polytetrafluoroethylene binder, and stirring for 1 hour until the mixture is uniformly dispersed to form colloid similar to dough; rolling a graphene electrode plate with the thickness of about 100-200 microns by a membrane rolling method;
step two, cutting the electrode into electrode slices of 10cm multiplied by 10cm, and drying for 18 hours at the temperature of 120 ℃ in vacuum;
placing the electrode slice on a sample frame of PECVD equipment, adjusting the distance between substrates to be 10cm, vacuumizing to 8 x 10-4Pa, setting the power to be 90W, introducing 10sccm silane and 30sccm hydrogen, and performing glow sputtering for 10min to prepare a self-supporting silicon-graphene composite cathode;
and step four, reversely placing the sample on a sample rack, and repeating glow sputtering to obtain the self-supporting double-sided silicon-graphene composite negative plate.
Example 3
A preparation method of a self-supporting double-sided silicon-graphene composite cathode is characterized in that the self-supporting double-sided silicon-graphene composite cathode, a lithium ion battery electrolyte and a cathode are assembled to form a lithium ion battery. The preparation process comprises the following steps:
step one, mixing 1g of graphene raw material with 0.1g of conductive agent (SP), adding 10ml of alcohol, stirring for 3 hours at normal temperature to uniformly mix the graphene raw material and the SP, adding 2ml of polytetrafluoroethylene binder, and stirring for 1 hour until the mixture is uniformly dispersed to form colloid similar to dough; rolling a graphene electrode plate with the thickness of about 100-200 microns by a membrane rolling method;
step two, cutting the electrode into electrode slices of 10cm multiplied by 10cm, and drying for 24 hours at the vacuum temperature of 150 ℃;
placing the electrode slice on a sample frame of PECVD equipment, adjusting the distance between substrates to be 10cm, vacuumizing to 8 x 10-4Pa, setting the power to be 100W, introducing 10sccm silane and 30sccm hydrogen, and performing glow sputtering for 15min to prepare a self-supporting silicon-graphene composite cathode;
and step four, reversely placing the sample on a sample rack, and repeating glow sputtering to obtain the self-supporting double-sided silicon-graphene composite negative plate.
Finally, assembling the self-supporting double-sided silicon-graphene composite negative plate prepared in the process, the lithium ion electrolyte and the phi 20 metal lithium plate into a lithium ion battery in an argon atmosphere glove box, and testing the battery performance in a blue test system, wherein the voltage range is 0.01V-2.5V, and the current density is 100mA g-1The test temperature was 25 ℃. Tests show that the first efficiency and the cycle performance of the battery are obviously improved.
Table 1 shows the first coulombic efficiencies of the self-supporting graphene negative electrode and the self-supporting double-sided silicon-graphene composite negative electrode in example 1 of the present invention.
| Self-supporting graphene cathode | Self-supporting double-sided silicon-graphene composite cathode | |
| First coulombic efficiency (%) | 82.93％ | 90.04％ |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of a self-supporting double-sided silicon-graphene composite cathode is characterized by comprising the following steps: the method comprises the following steps of,
s1, mixing the graphene material, the conductive agent and the binder in proportion, adding an organic solvent, stirring or ball-milling to form a precursor solution, and preparing a self-supporting graphene electrode plate in a membrane rolling manner;
s2, placing the self-supporting graphene electrode plate in a vacuum oven at the temperature of 100 ℃ and 150 ℃, and keeping for 12-24 h;
s3 self-supporting stonePlacing graphene electrode plate on sample rack in PECVD equipment, and vacuumizing to 8 x 10-4Pa；
S4, introducing silane and hydrogen into equipment, setting power to glow, decomposing silane gas and the like, bombarding a graphene electrode plate by utilizing silane plasma generated by glow, and doping silicon by utilizing a Plasma Enhanced Chemical Vapor Deposition (PECVD) method;
s5, reversely placing the self-supporting graphene electrode plate on the sample holder, and repeating the steps S3 and S4 to obtain the double-sided self-supporting silicon-graphene negative electrode plate.
2. The method for preparing the self-supporting double-sided silicon-graphene composite anode according to claim 1, wherein the step of preparing the self-supporting graphene electrode sheet in S1 is as follows: mixing a g of graphene raw material and b g of conductive agent, adding c ml of alcohol, stirring for 3 hours at normal temperature to uniformly mix, adding d ml of binder, and stirring for 1 hour until the mixture is uniformly dispersed to form a dough-like colloid; rolling a graphene electrode plate with the thickness of about 100-200 microns by a membrane rolling method; wherein a: b: c: d is 1:0.1:10: 2.
3. The method for preparing the self-supporting double-sided silicon-graphene composite negative electrode as claimed in claim 1, wherein the step of preparing the self-supporting silicon-graphene composite negative electrode in S4 is as follows: setting the glow starting power at 80-100W, introducing 10sccm silane and 30sccm hydrogen, and glow sputtering for 5-15 min.
4. The method for preparing the self-supporting double-sided silicon-graphene composite anode according to claim 1, wherein the method comprises the following steps: the graphene material is one or more combinations of graphene prepared from artificial graphite or natural graphite and graphene oxide.
5. The method for preparing the self-supporting double-sided silicon-graphene composite anode according to claim 1, wherein the method comprises the following steps: the conductive agent is one or a combination of acetylene black, Super P, Super S, 350G, carbon fiber, carbon nanotube, Ketjen black, graphite conductive agent and graphene.
6. The method for preparing the self-supporting double-sided silicon-graphene composite anode according to claim 1, wherein the method comprises the following steps: the binder is water-based or oil-based and comprises one or more of polytetrafluoroethylene, polyvinylidene fluoride, polyethylene oxide, polypropylene carbonate, polyethylene carbonate, polytrimethylene carbonate, polyvinyl alcohol, sodium carboxymethylcellulose, polyethylene, polypropylene and copolymers thereof, modified SBR, fluorinated rubber and polyurethane.
7. The method for preparing the self-supporting double-sided silicon-graphene composite anode according to claim 1, wherein the method comprises the following steps: the organic solvent is one or a combination of more of N-methyl-2-pyrrolidone, alcohol, tetrahydrofuran, propylene carbonate, dimethyl (ethyl) carbonate, methyl ethyl carbonate, ethyl acetate, acetonitrile, isopropyl ether, acetone, butanone, isopropanol, butanol, hexane, cyclohexane, N-dimethylacetamide, benzene, toluene, dimethyl sulfoxide, carbon tetrachloride, trichloroethylene and acetone.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111883761A (en) * | 2020-08-05 | 2020-11-03 | 重庆信合启越科技有限公司 | Silicon graphene composite lithium battery negative electrode material and preparation method thereof |
| CN114361384A (en) * | 2021-12-31 | 2022-04-15 | 远景动力技术(江苏)有限公司 | Negative electrode, electrochemical device, and electronic apparatus |
| CN114628665A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Battery cathode material and preparation method and application thereof |
| CN116169255A (en) * | 2021-11-25 | 2023-05-26 | 湖南中科星城石墨有限公司 | Silicon-carbon negative electrode material of lithium ion battery, and preparation method and application thereof |
| CN116682926A (en) * | 2022-02-22 | 2023-09-01 | 太仓中科赛诺新能源科技有限公司 | Porous self-supporting flexible thick electrode and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324497A (en) * | 2011-09-21 | 2012-01-18 | 上海大学 | A kind of graphene-supported carbon coats the preparation method of the lithium cell cathode material of tin antimony |
| US20130069011A1 (en) * | 2009-06-26 | 2013-03-21 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Doped-carbon nano-architectured structures and methods for fabricating same |
| CN103579589A (en) * | 2012-07-25 | 2014-02-12 | 海洋王照明科技股份有限公司 | Graphene-silicon-graphene composite material, preparation method of graphene-silicon-graphene composite material, lithium ion battery and preparation method of lithium ion battery |
| WO2015199251A1 (en) * | 2014-06-23 | 2015-12-30 | 동아대학교 산학협력단 | Nanoparticle-graphene-carbon composite having graphene network formed therein, preparation method therefor and application thereof |
| CN105304884A (en) * | 2015-05-18 | 2016-02-03 | 深圳市国创新能源研究院 | Graphene-based silicon-carbon composite anode material and preparation method thereof |
| US20170222219A1 (en) * | 2016-01-28 | 2017-08-03 | Dong Sun | Ordered nano-porous carbon coating on silicon or silicon/graphene composites as lithium ion battery anode materials |
| WO2018032974A1 (en) * | 2016-08-15 | 2018-02-22 | 福建新峰二维材料科技有限公司 | Method of preparing material of negative electrode of lithium ion battery |
| CN108878173A (en) * | 2018-05-25 | 2018-11-23 | 中国电子科技集团公司第十八研究所 | Preparation method of graphene positive plate heterojunction doping |
| CN109524641A (en) * | 2018-10-19 | 2019-03-26 | 西安科技大学 | Lithium ion battery flexible self-supporting silicon/graphene negative electrode material preparation method |
| CN109755508A (en) * | 2018-12-18 | 2019-05-14 | 湘潭大学 | A kind of preparation method of silicon/graphene MULTILAYER COMPOSITE membrane negative electrode material |
-
2019
- 2019-12-20 CN CN201911325025.8A patent/CN111081981A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130069011A1 (en) * | 2009-06-26 | 2013-03-21 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Doped-carbon nano-architectured structures and methods for fabricating same |
| CN102324497A (en) * | 2011-09-21 | 2012-01-18 | 上海大学 | A kind of graphene-supported carbon coats the preparation method of the lithium cell cathode material of tin antimony |
| CN103579589A (en) * | 2012-07-25 | 2014-02-12 | 海洋王照明科技股份有限公司 | Graphene-silicon-graphene composite material, preparation method of graphene-silicon-graphene composite material, lithium ion battery and preparation method of lithium ion battery |
| WO2015199251A1 (en) * | 2014-06-23 | 2015-12-30 | 동아대학교 산학협력단 | Nanoparticle-graphene-carbon composite having graphene network formed therein, preparation method therefor and application thereof |
| CN105304884A (en) * | 2015-05-18 | 2016-02-03 | 深圳市国创新能源研究院 | Graphene-based silicon-carbon composite anode material and preparation method thereof |
| US20170222219A1 (en) * | 2016-01-28 | 2017-08-03 | Dong Sun | Ordered nano-porous carbon coating on silicon or silicon/graphene composites as lithium ion battery anode materials |
| WO2018032974A1 (en) * | 2016-08-15 | 2018-02-22 | 福建新峰二维材料科技有限公司 | Method of preparing material of negative electrode of lithium ion battery |
| CN108878173A (en) * | 2018-05-25 | 2018-11-23 | 中国电子科技集团公司第十八研究所 | Preparation method of graphene positive plate heterojunction doping |
| CN109524641A (en) * | 2018-10-19 | 2019-03-26 | 西安科技大学 | Lithium ion battery flexible self-supporting silicon/graphene negative electrode material preparation method |
| CN109755508A (en) * | 2018-12-18 | 2019-05-14 | 湘潭大学 | A kind of preparation method of silicon/graphene MULTILAYER COMPOSITE membrane negative electrode material |
Non-Patent Citations (1)
| Title |
|---|
| FEI LI等: "Flexible free-standing graphene foam supported silicon films as high capacity anodes for lithium ion batteries", 《MATERIALS LETTERS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111883761A (en) * | 2020-08-05 | 2020-11-03 | 重庆信合启越科技有限公司 | Silicon graphene composite lithium battery negative electrode material and preparation method thereof |
| CN114628665A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Battery cathode material and preparation method and application thereof |
| CN114628665B (en) * | 2020-12-10 | 2024-02-02 | 中国科学院大连化学物理研究所 | Battery anode material and preparation method and application thereof |
| CN116169255A (en) * | 2021-11-25 | 2023-05-26 | 湖南中科星城石墨有限公司 | Silicon-carbon negative electrode material of lithium ion battery, and preparation method and application thereof |
| CN114361384A (en) * | 2021-12-31 | 2022-04-15 | 远景动力技术(江苏)有限公司 | Negative electrode, electrochemical device, and electronic apparatus |
| CN114361384B (en) * | 2021-12-31 | 2024-03-26 | 远景动力技术(江苏)有限公司 | Negative electrode, electrochemical device, and electronic apparatus |
| CN116682926A (en) * | 2022-02-22 | 2023-09-01 | 太仓中科赛诺新能源科技有限公司 | Porous self-supporting flexible thick electrode and preparation method thereof |
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