CN116002660B - Preparation method of carbon-silicon composite material, carbon-silicon composite material and lithium battery - Google Patents
Preparation method of carbon-silicon composite material, carbon-silicon composite material and lithium battery Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon-silicon composite material, the carbon-silicon composite material and application of the carbon-silicon composite material in a lithium battery cathode. The preparation method disclosed by the invention comprises the steps of modifying graphene oxide on the surface of a porous carbon substrate, hydrolyzing a silicon precursor in situ, roasting, mixing magnesium powder, performing thermal reduction treatment, and finally carrying out acid washing, water washing and drying. The preparation method can eliminate hot spots generated in the magnesium powder thermal reduction reaction, and effectively avoid the generation of silicon carbide byproducts. The carbon-silicon composite material obtained by the invention is applied to a lithium battery cathode, and the charge-discharge result shows that the reversible specific capacity is not lower than 1000mAh/g under the current density of 200mA/g, and the capacity can still be maintained to be more than 80% after 100 charge-discharge cycles, so that the carbon-silicon composite material has good cycle stability. The preparation method disclosed by the invention has the advantages of readily available raw materials, no toxicity, low cost, simple process, no special device, easiness in large-scale production, economy and practicability.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium battery anode materials, and particularly relates to a preparation method of a carbon-silicon composite material. In addition, the invention also relates to application of the carbon-silicon composite material as a negative electrode material of a lithium battery and a button lithium battery.
Background
With the rapid development of lithium ion battery cathode materials in recent years, graphite cathode materials with the theoretical capacity of 372mAh/g cannot meet the requirements of lithium ion batteries. Silicon has high theoretical capacity (4200 mAh/g), low potential for lithium and rich sources, but has overlarge volume change and poor ionic and electronic conductivity in the charge and discharge process, so that the silicon needs to be compounded with carbon to improve the conductivity and stability of the silicon. Although carbon-silicon composite materials have been developed into the most potential commercial anode materials of the new generation, the existing technology for preparing and further modifying carbon coating from nano silicon has high cost, complex process and unsuitable mass production.
US patent US10923722B2 discloses the large-scale preparation of silicon-carbon composites by silane gas chemical deposition using porous carbon channels as confinement spaces. The technology has the defects that the silane raw material has extremely toxic and explosive characteristics, and the production equipment is expensive, so that the technology is difficult to popularize in a large range. The porous carbon pore canal limited silicon oxide particles combined with the magnesia reduction reaction is expected to develop into a simple, low-cost and large-scale method for producing the silicon-carbon composite material, but the defects are that the magnesia reduction reaction is uncontrollable, the heat release is severe, the local hot spot is higher than 2000 ℃, the silicon and carbon are caused to react to further generate a large amount of silicon carbide byproducts (1800 ℃) and the electrochemical performance cannot be provided. In order to solve the technical problems, scientific researchers generally adopt the technical means that a large amount of molten salt moderator is added to control the magnesium thermal reaction temperature so as to further slow down the generation of silicon carbide byproducts, but at the same time, the novel technical problems of difficult impurity removal, more emission and high cost are brought.
Disclosure of Invention
The invention aims to solve the technical problems that silane gas has extremely toxic and explosive characteristics in the existing method for preparing a silicon-carbon composite material by taking porous carbon as a substrate through a chemical deposition method, and the method for preparing the silicon-carbon composite material by utilizing porous carbon pore-channel confined silicon oxide particles and combining a magnesia reduction reaction has uncontrollable magnesia thermal reaction and severe heat release, so that a large amount of silicon carbide byproducts are contained in the product to cause the product to lose electrochemical performance, and provides a novel preparation method of the silicon-carbon composite material.
In order to achieve the above object, the present invention adopts the following technical scheme.
A preparation method of a carbon-silicon composite material comprises the following steps:
s1, surface modification of porous carbon: weighing a proper amount of stearic acid coupling agent, adding the stearic acid coupling agent into the porous carbon powder, heating and stirring uniformly, then dripping a proper amount of graphene oxide solution, and sequentially grinding, ageing, drying and roasting to obtain a graphene oxide modified porous carbon substrate;
s2, silicon precursor load: introducing a silicon precursor into the porous carbon substrate prepared in the step S1 by adopting an impregnation method, slowly dropwise adding an alcohol ammonia solution for in-situ hydrolysis, and sequentially aging, drying and roasting to prepare an intermediate carbon material carrying the silicon precursor;
s3, heat reduction treatment: and (3) uniformly mixing the intermediate carbon material prepared in the step (S2) with a certain amount of metal magnesium powder, performing heat treatment under the protection of inert atmosphere, cooling to room temperature after the treatment is finished, and sequentially performing acid washing, water washing and drying treatment to obtain the carbon-silicon composite material of the porous carbon-loaded nano silicon.
Further, the porous carbon in S1 is preferably carbon black having quasicraphite crystallites as structural units.
Further, the weight ratio of the stearic acid coupling agent to the porous carbon powder in the S1 is 0.02-0.05; the weight ratio of the graphene oxide solution to the porous carbon is not less than 0.05.
Further, the silicon precursor in S2 is one or more of ethyl orthosilicate, sodium silicate and silica sol.
Further, the silicon precursor is preferably introduced into the porous carbon substrate using an isovolumetric impregnation method in S2.
Further, the alcohol ammonia solution in S2 is preferably an aqueous ammonia/ethanol solution.
Further, in the thermal reduction treatment process in S3, the weight ratio of the metal magnesium powder to the intermediate carbon material sample is preferably 0.5-2.0.
Further, in the heat reduction treatment process in S3, the heat treatment temperature is preferably 600-900 ℃, and the heat treatment time is preferably 2-8 hours.
The porous carbon loaded nano-silicon carbon-silicon composite material obtained by the preparation method is particularly suitable for serving as a battery anode material. A constant-current charge-discharge test is carried out on the lithium battery anode material containing the carbon-silicon composite material, the test current density is 200mA/g, the potential interval is 0.02-1.5V, and the test result shows that the lithium battery anode material has reversible specific capacity not lower than 1000mAh/g under the current density of 200mA/g, the initial coulomb efficiency is more than 90%, and the capacity retention rate is not lower than 80% after 100 weeks of circulation.
In addition, the invention also relates to a button lithium battery, and the negative electrode of the button lithium battery contains the carbon-silicon composite material. The preparation method of the lithium battery comprises the following steps: mixing a carbon-silicon composite material, conductive carbon black, a binder and a solvent according to a certain proportion to prepare slurry, coating the slurry on a copper foil, drying in a vacuum oven to prepare a pole piece, and then assembling the pole piece, a diaphragm, an electrolyte and a commercial lithium piece counter electrode together in a high-purity argon glove box to form the button cell.
A more specific technical scheme is as follows.
A preparation method of a carbon-silicon composite material comprises the following steps:
s1, adding 0.02-0.05 part by weight of stearic acid coupling agent into porous carbon powder, heating and stirring at 50-80 ℃, uniformly mixing, then dropwise adding an aqueous solution of graphene oxide, wherein the weight ratio of graphene oxide to porous carbon is not less than 0.05 part, grinding, ageing, drying overnight, and roasting at 300-500 ℃ for 1-3 hours under the protection of inert atmosphere to obtain a graphene oxide modified porous carbon substrate;
s2, introducing a silicon precursor into the graphene oxide modified porous carbon substrate prepared in the step S1 by adopting an isovolumetric impregnation method, slowly dropwise adding ammonia water/ethanol solution for in-situ hydrolysis, wherein the mass fraction of the silicon precursor is not higher than 50% in terms of silicon, aging the hydrolysate at 30-80 ℃ for 12 hours, drying overnight, and roasting at 300-500 ℃ for 0.5-2 hours in an air atmosphere to prepare an intermediate carbon material loaded with the silicon precursor;
and S3, weighing 0.5-2.0 weight of metal magnesium powder, mixing with the intermediate carbon material sample of the prepared silicon-loaded precursor prepared in the step S2, grinding uniformly under the protection of inert atmosphere, filling into a tubular reaction furnace, evacuating, cutting into flowing argon, heating to 600-900 ℃, performing heat treatment for 2-8 hours, cooling the sample, washing with 0.5-5M hydrochloric acid at room temperature, washing with water, and drying to obtain the porous carbon-loaded nano-silicon carbon-silicon composite material.
Preferably, the porous carbon in S1 is preferably carbon black having quasicraphite crystallites as structural units.
Preferably, the silicon precursor in S2 may be any one of ethyl orthosilicate, sodium silicate and silica sol. More preferably, the silicon precursor is ethyl orthosilicate.
The porous carbon-loaded nano silicon material obtained by the preparation method is particularly suitable for being used as a lithium battery anode material.
A button lithium battery is prepared by the following steps: mixing the carbon-silicon material, conductive carbon black, a binder and a solvent according to a certain proportion to prepare slurry, coating the slurry on a copper foil, drying the slurry overnight in a vacuum oven, and then assembling the slurry, a diaphragm, an electrolyte and a commercial lithium sheet counter electrode in a high-purity argon glove box to form the button cell. The prepared button cell is subjected to constant current charge and discharge test, and the result shows that the button cell has a reversible specific capacity of 1352 mAh/g under the current density of 200mA/g, is close to the theoretical capacity of the supported silicon active component, has a capacity retention rate of 89% after 100 weeks of circulation, and has good circulation stability.
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with the existing method for preparing the silicon-carbon composite material by taking porous carbon as a substrate through a chemical deposition method, the method provided by the invention has the characteristics of avoiding extremely toxic and explosive silane gas, and provides a preparation method of the carbon-silicon negative electrode material, which is simple in process, safe, reliable, economical and practical, for the field of lithium battery negative electrode manufacturing.
(2) Compared with the prior art that a huge amount of molten salt moderator is added to control the magnesia thermal reaction temperature, the preparation method of the invention eliminates hot spots generated in the magnesia thermal reduction reaction by compounding the heat conduction reinforcing material graphene oxide in the porous carbon substrate, effectively avoids the technical problem that silicon carbide byproducts are easy to generate in the silicon-carbon co-reduction process, and simultaneously does not need to remove a large amount of impurities brought by molten salt introduction.
(3) The carbon-silicon composite material obtained by the invention is used as a lithium battery cathode to obtain almost theoretical lithium storage capacity and good cycle stability, and compared with a silicon-carbon composite material prepared by a carbon substrate, the carbon-silicon composite material has the advantages of greatly improving electrochemical performance and good application effect as a lithium battery cathode. Compared with the existing mature silicon-carbon anode material preparation technology, the preparation method disclosed by the invention has the advantages of easily available raw materials, safety, no toxicity, simple process, no special device, easiness in large-scale production, less hybrid, low cost and economy and practicability.
Drawings
FIG. 1 is a powder X-ray diffraction pattern of the carbon-silicon composite material obtained in example 1 of the present invention and comparative example 1. X-ray powder diffraction analysis (figure 1) shows that the composite material prepared by the method mainly comprises diffraction peaks belonging to nano silicon crystal phases except the peaks of the porous carbon substrate, and the nano silicon crystal is well dispersed on the pore channel surfaces of the porous carbon substrate in the material.
FIG. 2 is a scanning transmission electron micrograph and an elemental Mapping of the carbon-silicon composite material obtained in example 1 of the present invention. The bright field (upper left BF in FIG. 2) and dark field (upper right ADF in FIG. 2) scanning transmission electron micrographs show that the porous carbon substrate has no large-scale silicon particle enrichment, which shows that the silicon dispersibility is good, and the spatial distribution of the combined element surface scanning analysis carbon (lower left C K in FIG. 2) and the silicon (lower right Si K in FIG. 2) is consistent, so that the silicon active phase is further uniformly distributed on the pore channel surface of the porous carbon substrate, and the structural characteristics ensure the efficiency of the silicon active substance to the greatest extent.
Detailed Description
In the examples of the present invention, the porous carbon material was commercially available ketjen black (product model ECP, ECP-600JD, shanghai Cuicake chemical engineering Co., ltd.) and amorphous mesoporous carbon was self-made (preparation method reference "Engineering Mesoporous Structure in Amorphous Carbon Boosts Potassium Storage with HighInitial Coulombic Efficiency", running Guo, et al, nano-Micro Lett. (2020) 12:148.). The present invention will be described in detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
(1) Weighing 0.02 g of stearic acid, adding 1.0 g of ketjen black powder, heating to 60 ℃ and mechanically stirring for 0.5 hour, taking out after uniform mixing, then weighing 5 ml of graphene oxide aqueous solution with the concentration of 0.01 g/ml, dripping into the mixture, stirring and grinding for 0.5 hour, ageing at room temperature for 12 hours, placing into a 120 ℃ oven for drying for 6 hours, and roasting at 350 ℃ for 2 hours under the protection of flowing nitrogen to obtain the ketjen black sample modified by graphene oxide.
(2) 2.232 g of ethyl orthosilicate is dissolved in 1.5 ml of absolute ethyl alcohol, immersed on 1.0 g of graphene oxide modified ketjen black sample, kept stand for 0.5 hour at room temperature and then added with a proper amount of ammonia water 50 in a dropwise mannerAging for 12 hr, drying at 120deg.C for 6 hr, and placing in muffle furnace 350 ∈ ->And C, roasting 2 h to obtain the silicon-precursor-loaded Ketjen black sample.
(3) Weighing 0.8 g of metal magnesium powder under the protection of argon, grinding and mixing with 1.0 g of Keqin black sample of the load silicon precursor, filling into a tubular reaction furnace, vacuumizing, cutting into 40 ml of argon with the flow rate of 40 ml per minute, heating to 700 ℃ at the rate of 5 ℃ per minute, and performing heat treatment for 4 hours; and (3) washing and filtering the sample after cooling the sample by using a 2M hydrochloric acid solution, washing and filtering the sample by using deionized water, and drying the sample at 120 ℃ for 6 hours to obtain the ketjen black-loaded nano silicon material.
(4) The prepared carbon-silicon composite material is used as an active substance, and is mixed with conductive carbon black and polyvinylidene fluoride according to the following proportion of 6:2:2, adding a proper amount of N-methyl pyrrolidone solvent to prepare slurry after mixing according to the mass ratio, uniformly coating the slurry on a copper foil by using a coating machine, vacuum drying in a vacuum oven at 60 ℃ for 6 hours to prepare a pole piece, baking at 100 ℃ for 2 hours, and vacuum drying in a vacuum drying oven at 80 ℃ for 12 hours.
(5) And assembling the baked negative plate, the polypropylene diaphragm, the lithium hexafluorophosphate electrolyte and the commercial lithium plate counter electrode together in a high-purity argon glove box to form a button cell, and performing charge and discharge test, wherein the current density is 200mA/g, the potential interval is 0.02-1.5V, and the evaluation result is shown in Table 1.
Example 2
The preparation and evaluation were carried out by the method of example 1 except that the amount of the aqueous graphene oxide solution used in the step (1) was 10 ml, and the lithium electrical properties were evaluated as shown in Table 1.
Example 3
The preparation and evaluation were carried out by the method of example 1 except that the amount of the aqueous graphene oxide solution used in the step (1) was 1 ml, and the lithium electrical properties were evaluated as shown in Table 1.
Example 4
The preparation and evaluation were performed by the method of example 1, except that the silicon precursor in the step (2) was water glass, and the lithium electrical property evaluation results are shown in Table 1.
Example 5
The preparation and evaluation were performed by the method of example 1, except that the silicon precursor in the step (2) was silica sol, and the lithium electrical property evaluation results are shown in table 1.
Example 6
The preparation and evaluation were carried out by the method of example 1 except that the amorphous mesoporous carbon was used instead of ketjen black in step (1), and the lithium electrical properties were evaluated as shown in Table 1.
Comparative example 1
The procedure of example 1 was used for the preparation and evaluation, except that the black surface of ketjen was not modified with graphene oxide, but was directly impregnated with a silicon precursor, and the lithium electrical properties were evaluated as shown in table 1.
TABLE 1 lithium electrical property test results for examples 1-5 and comparative example 1
As shown in Table 1, the carbon-silicon composite material prepared in the embodiment 1 of the invention is used as a lithium battery cathode to obtain almost theoretical lithium storage capacity, has a reversible specific capacity of 1352 mAh/g under 200mA/g current density, has a first coulomb efficiency of 90.6%, has a capacity retention rate of 87% after 100 weeks of circulation, and has good circulation stability. When the graphene oxide is used in an insufficient amount (example 3) in the preparation of the carbon-silicon composite material, the electrochemical performance is poor, and when the graphene oxide is used in an excessive amount (example 2), the effect is not better than that of example 1. The electrochemical test results of examples 4 and 5 further show that a variety of silicon precursors are suitable for use in the preparation methods of the present invention. Example 6 shows that the preparation method of the invention is also applicable to other porous-like carbons.
Claims (8)
1. The preparation method of the carbon-silicon composite material is characterized by comprising the following steps:
s1, surface modification of porous carbon: weighing a proper amount of stearic acid coupling agent, adding the stearic acid coupling agent into porous carbon powder, heating and stirring uniformly, then dripping a proper amount of graphene oxide solution, and sequentially grinding, ageing, drying and roasting under the protection of flowing nitrogen to prepare a graphene oxide modified porous carbon substrate; the porous carbon is carbon black taking quasi-graphite microcrystals as structural units; the weight ratio of the stearic acid coupling agent to the porous carbon powder is 0.02-0.05; the weight ratio of the graphene oxide to the porous carbon is not less than 0.05;
s2, silicon precursor load: introducing a silicon precursor into the porous carbon substrate prepared in the step S1 by adopting an impregnation method, slowly dropwise adding an alcohol ammonia solution for in-situ hydrolysis, and aging, drying and roasting after the hydrolysis is finished to prepare an intermediate carbon material carrying the silicon precursor;
s3, heat reduction treatment: and (3) uniformly mixing the intermediate carbon material prepared in the step (S2) with a certain amount of metal magnesium powder, performing heat treatment under the protection of inert atmosphere, cooling to room temperature after the treatment is finished, and sequentially performing acid washing, water washing and drying treatment to obtain the carbon-silicon composite material of the porous carbon-loaded nano-silicon.
2. The method for preparing the carbon-silicon composite material according to claim 1, wherein the method comprises the following steps: and S2, the silicon precursor is one or more of tetraethoxysilane, sodium silicate and silica sol.
3. The method for preparing the carbon-silicon composite material according to claim 1, wherein the method comprises the following steps: in S2, an isovolumetric impregnation method is used to introduce the silicon precursor into the porous carbon substrate.
4. The method for preparing the carbon-silicon composite material according to claim 1, wherein the method comprises the following steps: the alcohol ammonia solution in S2 is ammonia water/ethanol solution.
5. The method for preparing the carbon-silicon composite material according to claim 1, wherein the method comprises the following steps: in the thermal reduction treatment process in the step S3, the weight ratio of the metal magnesium powder to the intermediate carbon material sample is 0.5-2.0.
6. The method for preparing the carbon-silicon composite material according to claim 1, wherein the method comprises the following steps: in the heat reduction treatment process in the step S3, the heat treatment temperature is 600-900 ℃, and the heat treatment time is 2-8 h.
7. The carbon-silicon composite material obtained by the preparation method of claim 1 is used as a lithium battery cathode, and is subjected to constant current charge and discharge test, wherein the test current density is 200mA/g, the potential interval is 0.02-1.5V, and the test result shows that: the reversible specific capacity of not less than 1000mAh/g is achieved under the current density of 200mA/g, the initial coulomb efficiency reaches more than 90%, and the capacity retention rate is not less than 80% after 100 weeks of circulation.
8. A button lithium battery, characterized in that: the negative electrode of the lithium battery comprises the carbon-silicon composite material of claim 7; the preparation method of the lithium battery comprises the following steps: mixing a carbon-silicon composite material, conductive carbon black, a binder and a solvent according to a certain proportion to prepare slurry, coating the slurry on a copper foil, drying in a vacuum oven to prepare a pole piece, and then assembling the pole piece, a diaphragm, an electrolyte and a commercial lithium piece counter electrode together in a high-purity argon glove box to form the button cell.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106941164A (en) * | 2017-04-11 | 2017-07-11 | 东南大学 | A kind of preparation method of lithium ion battery negative nucleocapsid clad structure material |
| WO2017190417A1 (en) * | 2016-05-06 | 2017-11-09 | 清华大学深圳研究生院 | Method for preparing thick and dense graphene-based electrode |
| CN107959013A (en) * | 2017-11-20 | 2018-04-24 | 清华大学 | The carbon-silicon composite material of graphene coated silicon grain and its preparation and application |
| WO2018081708A1 (en) * | 2016-10-31 | 2018-05-03 | The Board Of Trustees Of The University Of Illinois | Silicon composite electrodes with dynamic ionic bonding |
| CN108172801A (en) * | 2017-12-28 | 2018-06-15 | 哈尔滨工业大学深圳研究生院 | A kind of method of porous carbon materials doping vario-property and application |
| CN108630919A (en) * | 2018-04-04 | 2018-10-09 | 合肥国轩高科动力能源有限公司 | A kind of carbon coating silicon/graphene complex and its preparation method and application |
| WO2019027337A1 (en) * | 2017-08-04 | 2019-02-07 | Instytut Niskich Temperatur I Badan Strukturalnych Pan Im.W.Trzebiatowskiego | Stable graphene-silica composites and the method for manufacturing thereof |
| CN109659154A (en) * | 2018-12-26 | 2019-04-19 | 武汉工程大学 | A kind of preparation method and applications of Carbon-based supercapacitor electrode material |
| CN110010861A (en) * | 2019-03-07 | 2019-07-12 | 南方科技大学 | Silicon based composite material and preparation method thereof, lithium ion battery |
| CN112054171A (en) * | 2020-08-13 | 2020-12-08 | 利普同呈(江苏)新能源科技有限公司 | Carbon-silicon negative electrode material and preparation method thereof |
| CN112909255A (en) * | 2021-01-20 | 2021-06-04 | 南京师范大学 | Silicon-silicon carbide/graphene composite material and preparation method thereof |
| CN113675392A (en) * | 2021-07-28 | 2021-11-19 | 四川九源芯材料科技有限公司 | Porous silicon-carbon composite material and preparation method and application thereof |
| CN113707858A (en) * | 2021-08-23 | 2021-11-26 | 上海颂柏智能技术开发中心 | Porous carbon-silicon composite negative electrode material and preparation method thereof |
| WO2022012075A1 (en) * | 2020-07-14 | 2022-01-20 | 广东工业大学 | Porous carbon-graphene composite material and preparation method therefor |
| WO2022029423A1 (en) * | 2020-08-03 | 2022-02-10 | Nexeon Limited | Electroactive materials for metal-ion batteries |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102881871A (en) * | 2012-10-11 | 2013-01-16 | 路密 | Method for preparing graphite/silicone composite material for negative electrode of lithium ion battery |
| CN109103443B (en) * | 2018-08-08 | 2020-10-27 | 欣旺达电子股份有限公司 | Silicon-based negative electrode material and preparation method thereof |
| CN112047323B (en) * | 2020-09-01 | 2021-11-26 | 四川大学 | Carbonized grapefruit pulp @ silicon @ rGO natural electromagnetic shielding material and preparation method and application thereof |
| CN112382740A (en) * | 2020-09-30 | 2021-02-19 | 银隆新能源股份有限公司 | Graphene-like carbon coated silicon/carbon/graphene composite material, preparation method thereof and negative electrode material |
| CN113299896B (en) * | 2021-05-27 | 2022-05-31 | 齐鲁工业大学 | Preparation method and application of hollow porous silicon-carbon @ lignin-carbon nanospheres |
-
2022
- 2022-12-28 CN CN202211712475.4A patent/CN116002660B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017190417A1 (en) * | 2016-05-06 | 2017-11-09 | 清华大学深圳研究生院 | Method for preparing thick and dense graphene-based electrode |
| WO2018081708A1 (en) * | 2016-10-31 | 2018-05-03 | The Board Of Trustees Of The University Of Illinois | Silicon composite electrodes with dynamic ionic bonding |
| CN106941164A (en) * | 2017-04-11 | 2017-07-11 | 东南大学 | A kind of preparation method of lithium ion battery negative nucleocapsid clad structure material |
| WO2019027337A1 (en) * | 2017-08-04 | 2019-02-07 | Instytut Niskich Temperatur I Badan Strukturalnych Pan Im.W.Trzebiatowskiego | Stable graphene-silica composites and the method for manufacturing thereof |
| CN107959013A (en) * | 2017-11-20 | 2018-04-24 | 清华大学 | The carbon-silicon composite material of graphene coated silicon grain and its preparation and application |
| CN108172801A (en) * | 2017-12-28 | 2018-06-15 | 哈尔滨工业大学深圳研究生院 | A kind of method of porous carbon materials doping vario-property and application |
| CN108630919A (en) * | 2018-04-04 | 2018-10-09 | 合肥国轩高科动力能源有限公司 | A kind of carbon coating silicon/graphene complex and its preparation method and application |
| CN109659154A (en) * | 2018-12-26 | 2019-04-19 | 武汉工程大学 | A kind of preparation method and applications of Carbon-based supercapacitor electrode material |
| CN110010861A (en) * | 2019-03-07 | 2019-07-12 | 南方科技大学 | Silicon based composite material and preparation method thereof, lithium ion battery |
| WO2022012075A1 (en) * | 2020-07-14 | 2022-01-20 | 广东工业大学 | Porous carbon-graphene composite material and preparation method therefor |
| WO2022029423A1 (en) * | 2020-08-03 | 2022-02-10 | Nexeon Limited | Electroactive materials for metal-ion batteries |
| CN112054171A (en) * | 2020-08-13 | 2020-12-08 | 利普同呈(江苏)新能源科技有限公司 | Carbon-silicon negative electrode material and preparation method thereof |
| CN112909255A (en) * | 2021-01-20 | 2021-06-04 | 南京师范大学 | Silicon-silicon carbide/graphene composite material and preparation method thereof |
| CN113675392A (en) * | 2021-07-28 | 2021-11-19 | 四川九源芯材料科技有限公司 | Porous silicon-carbon composite material and preparation method and application thereof |
| CN113707858A (en) * | 2021-08-23 | 2021-11-26 | 上海颂柏智能技术开发中心 | Porous carbon-silicon composite negative electrode material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Monodisperse Porous Silicon Spheres as Anode Materials for Lithium Ion Batteries;Wei Wang 等;《SCIENTIFIC REPORTS》;第1-6页 * |
| Synthesis, characterization and electrical properties of silicon-doped graphene films;Zegao Wang 等;《Journal of Materials Chemistry C》;第1-7页 * |
| 多孔碳质材料在氧还原电催化中的应用;杨慧聪 等;新型炭材料(03);第1-4页 * |
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