CN111370656A - Silicon-carbon composite material and preparation method and application thereof - Google Patents
Silicon-carbon composite material and preparation method and application thereof Download PDFInfo
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- CN111370656A CN111370656A CN201811604176.2A CN201811604176A CN111370656A CN 111370656 A CN111370656 A CN 111370656A CN 201811604176 A CN201811604176 A CN 201811604176A CN 111370656 A CN111370656 A CN 111370656A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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 relates to a silicon-carbon composite material and a preparation method and application thereof, wherein the silicon-carbon composite material comprises a first two-dimensional carbon nano material layer, a two-dimensional silicon nano material layer and a second two-dimensional carbon nano material layer which are stacked from top to bottom. The preparation method has the advantages of low cost and easy obtainment of raw materials, simple preparation process, low energy consumption and capability of amplification, and the prepared composite material has excellent electron/lithium ion transmission characteristics and structure/interface stability and shows excellent charge-discharge specific capacity and cycle stability as a battery cathode material.
Description
Technical Field
The invention belongs to the technical field of battery manufacturing, and particularly relates to a silicon-carbon composite material and a preparation method and application thereof.
Background
With the increasing exhaustion of fossil fuels and the rapid development of portable electronic devices and electric vehicles, the research on new energy sources such as power source batteries has become a focus of global attention, and lithium ion batteries have been widely used due to their excellent characteristics such as high energy density, high power density, good cycle performance, environmental friendliness, diversified structures, and low price. The structure of a lithium ion battery is mainly composed of a positive electrode, a negative electrode, a separator and an electrolyte, and whether the electrode performance of a negative electrode material can be further improved becomes a determining factor that restricts the performance of the lithium ion battery.
Aiming at the development requirements of the lithium ion power battery, the negative electrode material is objectively required to have the characteristics of high capacity, rapid charge and discharge, high thermal stability, low manufacturing cost and the like. At present, most of negative electrode materials in practical application are carbon materials, such as natural graphite, graphitized mesocarbon microbeads and the like, wherein the theoretical capacity of the graphite negative electrode material is 372mAh/g, the actual capacity is 320 mAh/g and 350mAh/g, the high-rate charge-discharge performance is poor, and the development of a lithium ion battery in the aspects of high capacity and high power is limited.
Silicon has higher capacity and excellent rate performance compared with graphite as a secondary battery cathode active material with great development prospect, especially for lithium ion batteries. However, the silicon material is accompanied by a great volume change during charge and discharge, and the generated mechanical stress causes pulverization and structural collapse of the active material to further cause detachment between the active materials and between the active material and a current collector, thereby causing rapid capacity fading and degradation of battery cycle performance. Meanwhile, due to the volume expansion effect of the silicon material, the silicon is difficult to form a stable solid electrolyte interface SEI film at an interface contacting with an electrolyte, so that the consumption of an active material and the charge-discharge efficiency are reduced, and the deterioration of the cycle performance is further accelerated. In order to solve the problems mentioned above, the silicon material is nanostructured and/or porous, and then is compounded with the carbon nano material to construct the silicon-carbon nano composite material, so that the problem of instability of a structure and a surface interface caused by a volume expansion effect in the charge and discharge process of silicon can be solved to a certain extent, and the charge and discharge and cycle performance of the silicon can be improved. However, in the constructed silicon-carbon composite material, a cavity (such as a classic egg-yolk shell structure/tube center line structure) must be introduced or reserved between the silicon component and the carbon component to relieve the great volume expansion of silicon in the charging and discharging processes, so that the damage of the carbon component and other electrode components is effectively avoided. The effective structural design improves the material structure and interface stability, but the resulting insufficient contact between silicon and carbon phases (point-to-point contact or line-to-line contact) seriously hinders the electron/lithium ion transmission and inhibits the improvement of the lithium storage performance of the material.
CN102891297A discloses a silicon-carbon composite material for a lithium ion battery and a preparation method thereof, which belong to the field of lithium ion batteries, wherein sodium carboxymethylcellulose is used as a binder, a liquid phase coating technology is utilized for silicon-carbon compounding, and a spray drying technology is utilized for drying and granulating to prepare the silicon-carbon composite material for the lithium ion battery with uniform granularity and excellent performance. The lithium ion battery composite material is prepared by adopting a silicon-carbon composite technology, the capacity is higher than that of the traditional graphite cathode material and reaches more than 500mAh/g, the pulverization phenomenon caused by silicon in the charging and discharging process can be prevented, and the cycle performance of the silicon-carbon composite material is effectively improved; the silicon-carbon material has uniform particles and small specific surface area, improves the cycle performance of the silicon-carbon composite material, but the insufficient contact of the silicon and the carbon seriously affects the electron/lithium ion transmission performance, and inhibits the improvement of the lithium storage performance of the material.
CN108807896A discloses a preparation method of a nitrogen-doped carbon-coated silicon-carbon composite material, which comprises the following steps: mixing melamine, organic acid and modified graphene in a solvent by taking the melamine as a nitrogen source, the organic acid as a carbon source and the modified graphene as a conductive bridge, adding a silicon-carbon material, mixing and drying; grinding and sieving, transferring the material into a rotary furnace, introducing inert atmosphere, heating, and coating functional structural components generated in situ after the reaction of melamine, organic acid and modified graphene on the surface of the silicon-carbon composite material to obtain the uniformly coated nitrogen-doped carbon-coated silicon-carbon composite material. The material has the advantages of obviously improved cycle performance and good rate capability. The method is simple, low in cost and very suitable for large-scale production and application, but the electron/lithium ion transmission characteristics of the silicon-carbon composite material are still limited.
CN106058207A discloses a method for preparing a silicon-carbon composite material, the method comprising: introducing a mixed gas consisting of silicon tetrachloride gas and a reduction carrier gas into a reaction chamber in which a carbon material is placed, wherein the reduction carrier gas contains a reducing gas; heating the mixed gas so that the reducing gas reduces the silicon tetrachloride gas to elemental silicon, and forming a silicon-carbon composite in which the elemental silicon is deposited on the carbon material. The method has the advantages of cheap raw materials, simple process and excellent product performance. The present invention also provides a silicon carbon composite material and a negative electrode for a lithium ion battery comprising the same, but insufficient contact of the silicon carbon structure also seriously hinders the electron/lithium ion transport properties thereof.
Therefore, it is an urgent problem to find a silicon-carbon composite material with excellent electron/lithium ion transmission characteristics and structure/interface stability, and with simple preparation process, large-scale production and low cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a silicon-carbon composite material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a silicon-carbon composite material, which is characterized in that the silicon-carbon composite material includes a first two-dimensional carbon nanomaterial layer, a two-dimensional silicon nanomaterial layer, and a second two-dimensional carbon nanomaterial layer stacked from top to bottom.
According to the invention, the two-dimensional carbon nanomaterial, the two-dimensional silicon nanomaterial and the two-dimensional carbon nanomaterial are compounded in a face-to-face contact manner to form a sandwich-shaped structure, so that the volume expansion of silicon in the charging and discharging processes can be relieved, the damage of carbon components and other components can be effectively avoided, and the structure and interface stability of the material can be improved; silicon and carbon can be fully contacted, the electron/lithium ion transmission performance is promoted, and the lithium storage performance of the material is greatly improved; meanwhile, the high conductivity, high chemical and mechanical stability of the two-dimensional carbon nano material further promotes the electron/lithium ion transmission performance of the material; the total shows excellent specific charge-discharge capacity and cycling stability.
Preferably, the silicon content of the silicon-carbon composite material is 30-99% by weight, such as 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90% or 99%, etc., preferably 50-80%.
The weight percentage of silicon in the silicon-carbon composite material is specifically selected within the range of 30-99%, because when the weight percentage is less than 30%, the specific capacity of the material is low, which is not beneficial to the improvement of the integral energy density of the battery; when the percentage content is more than 99%, the cycle stability is poor, the interface stability is poor, and the service life of the battery is shortened; and when the percentage content is 50-80%, the optimum effects of specific capacity, cycle performance and rate capability are achieved.
Preferably, the thickness of the two-dimensional silicon nanomaterial layer is 0.5-1000nm, such as 0.5nm, 1nm, 10nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, or the like, preferably 10-50 nm.
The thickness of the two-dimensional silicon nano material layer is specially selected within the range of 0.5-1000nm, because when the thickness is less than 0.5nm, the material preparation process is complicated, and the cost is increased; when the thickness is more than 1000nm, the pulverization of the material is caused, and the cycle stability is reduced; when the thickness is 10-50nm, the cycling stability and electron/lithium ion transport property have the best effect.
Preferably, the ratio of the length of the short side of the two-dimensional silicon nanomaterial layer to the thickness is 1-1000, such as 1, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900 or 1000, etc., preferably 10-100.
The length-diameter ratio of the two-dimensional silicon nano material layer is specially selected to be in the range of 1-1000, because when the length-diameter ratio is less than 1, the tap density of the material is low, and the volume energy density of the battery is reduced; when the length-diameter ratio is more than 1000, pulverization of the material is caused, and the cycle stability is reduced; when the length-diameter ratio is in the range of 10-100, the high-volume energy density high-cycle-life high-rate performance high-volume energy density high-cycle-life high-rate performance high.
Preferably, the surface of the two-dimensional silicon nano material layer is modified with a carbonized and/or denatured dispersant.
The carbonization refers to carbonizing a carbon-containing precursor at a high temperature to obtain a two-dimensional carbon coating layer; denaturation refers to the modification of the structure of the dispersant by low temperature treatment, which maintains the polymer properties of the polymer material and improves the conductivity.
The carbonized and/or denatured dispersant is modified on the surface of the two-dimensional silicon nano material, so that the two-dimensional carbon nano material can be dispersed more uniformly and controllably.
Preferably, the dispersant includes any one or a combination of at least two of glucose, sucrose, fructose, maltose, chitosan, citric acid, urea, ascorbic acid, starch, protein, gelatin, gum arabic, alginate, cellulose, phenolic resin, polyvinylidene fluoride, polyamino acid, polyvinylpyrrolidone, polycarbonate, polyvinyl alcohol, polyethylene glycol, polymethyl methacrylate, polyethyl methacrylate, polyacrylic resin, polyvinyl chloride, polyacrylonitrile, polylactic acid, or polystyrene, for example, a combination of glucose and sucrose, chitosan and polyvinylidene fluoride, alginate and polyethylene glycol, polylactic acid and polystyrene, and the like.
In the present invention, the two-dimensional carbon nanomaterial includes any one of graphene, graphene oxide, reduced graphene oxide, or amorphous two-dimensional carbon nanomaterial, or a combination of at least two of the two, such as graphene and graphene oxide, graphene oxide and reduced graphene oxide, graphene and reduced graphene oxide, and the like.
Preferably, the amorphous two-dimensional carbon nanomaterial comprises a material obtained by carbonizing polyacrylic resin, polyvinyl chloride or polyacrylonitrile.
The two-dimensional carbon nanomaterial has high conductivity, high chemical stability and high mechanical stability, is a high-efficiency transmission medium for electrons/lithium ions, and can improve the electron/lithium ion transmission performance of the silicon-carbon composite material.
In a second aspect, the present invention provides a method for preparing the above silicon-carbon composite material, wherein the method comprises:
assembling the two-dimensional carbon nanomaterial on the upper and lower layers of the two-dimensional silicon nanomaterial layer by a chemical vapor deposition method or a chemical assembly method to obtain the silicon-carbon composite material.
The preparation method does not need any substrate, template or other non-electrochemical active auxiliary materials, directly starts from a two-dimensional silicon nano material with a self-supporting structure, and prepares the sandwich-shaped silicon-carbon composite material by a chemical deposition method or a chemical assembly method.
Preferably, the two-dimensional carbon nanomaterial is graphene, and the two-dimensional carbon nanomaterial is assembled on the upper and lower layers of the two-dimensional silicon nanomaterial layer by a chemical vapor deposition method. Under the non-oxidizing atmosphere, methane is used as a carbon source, and the graphene two-dimensional carbon nanomaterial with high quality and uniform dispersion can be obtained on the surface of the two-dimensional silicon nanomaterial.
Preferably, the two-dimensional carbon nanomaterial is graphene oxide, reduced graphene oxide, or an amorphous two-dimensional carbon nanomaterial, and the two-dimensional carbon nanomaterial is assembled on the upper and lower layers of the two-dimensional silicon nanomaterial layer by a chemical assembly method. The graphene oxide, the reduced graphene oxide or the amorphous two-dimensional carbon nanomaterial realizes uniform compounding with the two-dimensional silicon material through electrostatic interaction by utilizing rich functional groups on the surface of the graphene oxide, the reduced graphene oxide or the amorphous two-dimensional carbon nanomaterial.
Preferably, the two-dimensional silicon nanomaterial is prepared by a magnesiothermic reduction method, a chemical oxidation stripping method or a physical vapor deposition method.
Preferably, the atmosphere conditions of the chemical vapor deposition method include any one or a combination of at least two of nitrogen, argon, hydrogen, helium, or carbon dioxide.
Preferably, the atmosphere condition of the chemical vapor deposition method is a mixed gas of hydrogen and argon.
Preferably, H in the mixed gas2The concentration of (A) is 5% -95%.
Preferably, the ventilation rate of the chemical vapor deposition method is 80-100sccm, such as 80sccm, 85sccm, 88sccm, 90sccm, 95sccm, 98sccm, or 100 sccm.
Preferably, the temperature rise rate of the chemical vapor deposition method is 5-10 ℃/min, such as 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, or 10 ℃/min, and the like.
Preferably, the deposition temperature of the chemical vapor deposition method is 900-.
Preferably, the holding time of the chemical vapor deposition method is 10-30min, such as 10min, 12min, 15min, 17min, 20min, 23min, 25min, 28min or 30 min.
Preferably, the atmosphere conditions of the chemical assembling method include any one or a combination of at least two of nitrogen, argon, hydrogen, helium, or carbon dioxide.
Preferably, the atmosphere condition of the chemical assembling method is a mixed gas of hydrogen and argon.
Preferably, H in the mixed gas2The concentration of (A) is 5% -95%.
Preferably, the thermal treatment ventilation rate of the chemical assembly method is 80-500sccm, such as 80sccm, 90sccm, 150sccm, 200sccm, 300sccm, 405sccm, 450sccm, or 500 sccm.
Preferably, the temperature rise rate of the heat treatment of the chemical assembly method is 1-50 ℃/min, such as 1 ℃/min, 5 ℃/min, 8 ℃/min, 15 ℃/min, 25 ℃/min, 35 ℃/min, 45 ℃/min or 50 ℃/min.
Preferably, the heat-preservation temperature of the heat treatment in the chemical assembly method is 300-.
Preferably, the heat treatment of the chemical assembly method has a holding time of 5-600min, such as 5min, 10min, 20min, 50min, 100min, 200min, 320min, 450min, 510min or 600 min.
In a third aspect, the present invention provides a battery anode material comprising a silicon carbon composite as described above.
Preferably, the mass of the silicon-carbon composite material is not less than 1% of the total mass of the battery negative electrode material, and when the silicon-carbon composite material is mixed with other active negative electrode materials to be used as the battery negative electrode material, the mass percentage of the silicon-carbon composite material to be used as the battery negative electrode material is not less than 1%, and if the mass percentage is less than 1%, the energy density of the battery is low.
Other active negative electrode materials may be artificial graphite, natural graphite, hard carbon materials, single-walled carbon nanotubes, few-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, reduced graphene oxide, metals and their precursors (tin, germanium, aluminum, cobalt, etc.) that can undergo an alloying reaction with lithium, transition metal compounds (cobalt oxide, iron oxide, titanium oxide, zinc oxide, tin oxide, etc.) that can undergo a conversion reaction with lithium, and lithium intercalation-type transition metal oxides (lithium titanate, etc.).
In a fourth aspect, the present invention provides an electrochemical energy storage device comprising a silicon carbon composite as described above.
Preferably, the electrochemical energy storage device is a lithium ion battery, and the lithium ion battery has excellent charge-discharge specific capacity and cycling stability.
Compared with the prior art, the invention has the following advantages:
the sandwich-like silicon-carbon composite material has excellent electron/lithium ion transmission characteristics and structure/interface stability. Specifically, the volume expansion of silicon in the charging and discharging processes can be relieved, the damage of carbon components and other components can be effectively avoided, and the structure and interface stability of the material can be improved; silicon and carbon can be fully contacted, so that the electron/lithium ion transmission performance is promoted, and the lithium storage performance of the material is greatly improved; meanwhile, the high conductivity, high chemical and mechanical stability of the two-dimensional carbon nanomaterial further promotes the electron/lithium ion transmission performance of the material; the material as a battery cathode material shows excellent charge-discharge specific capacity and cycling stability, has the gravimetric specific capacity as high as 2142mAh/g under the current density of 0.5C, and has the capacity retention rate as high as 91 percent after being cycled for 1000 times.
The preparation method of the sandwich-shaped silicon-carbon composite material does not need any substrate, template or other non-electrochemical active auxiliary materials, and directly starts from the two-dimensional silicon nano material with the self-supporting structure to prepare the sandwich-shaped silicon-carbon composite material by a chemical deposition method or a chemical assembly method.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
Example 1
The embodiment provides a silicon-carbon composite material, which comprises a two-dimensional carbon nano material, a two-dimensional silicon nano material and a two-dimensional carbon nano material which are compounded from top to bottom in a face-to-face manner, wherein the mass percentage of silicon in the silicon-carbon composite material is 96%, the thickness of the two-dimensional silicon nano material is 6nm, and the ratio of the side length of a short side to the thickness of the short side is 15. The preparation method comprises the following steps: putting the two-dimensional silicon nano material prepared by the magnesiothermic reduction method into a high-temperature tube furnace, vacuumizing by a vacuum device, replacing argon, repeating for 3 times, and ensuring an oxygen-free environment; run the apparatus at 100sccm H2Mixed gas of/Ar (H)2The volume fraction of (1) is 5%), heating to 1100 deg.C at a rate of 5 deg.C/min, and introducing CH at a rate of 50sccm4And preserving the temperature for 20min, and depositing the graphene on the two-dimensional silicon nano material to obtain the silicon-carbon composite material.
The embodiment also provides a battery cathode material prepared from the silicon-carbon composite material and a lithium ion battery using the cathode material as the battery cathode material, and the preparation method comprises the following steps: mixing a silicon-carbon composite material, conductive carbon black and sodium alginate according to a ratio of 8:1:1 to prepare slurry, coating the slurry on a copper foil, drying the slurry for 2 hours at 70 ℃, cutting the slurry into pole pieces with the diameter of 12mm by using a slicing machine, taking a metal lithium foil as a counter electrode, taking an electrolyte as a 1M mixed solvent (the volume ratio of the front solvent to the rear solvent is 1:1) of ethylene carbonate and diethyl carbonate in which lithium hexafluorophosphate is dissolved, and assembling the diaphragm as Celgard 2400 to obtain the button type lithium ion battery.
The performance of the battery is tested, and the test result is as follows: the gravimetric specific capacity is 2142mAh/g under the current density of 0.5C; after 1000 cycles, the capacity retention rate was 91%.
Example 2
The embodiment provides a silicon-carbon composite material, which comprises a two-dimensional carbon nano material and a two-dimensional silicon nano which are compounded from top to bottom in a face-to-face mannerThe silicon-carbon composite material comprises a rice material and a two-dimensional carbon nano material, wherein the mass percentage of silicon in the silicon-carbon composite material is 82%, the thickness of the two-dimensional silicon nano material is 5.4nm, and the ratio of the side length of a short side to the thickness of the short side is 20. The preparation method comprises the following steps: dispersing a two-dimensional silicon nano material prepared by a chemical oxidation stripping method in a 1% glucose aqueous solution, adding graphene oxide, performing ultrasonic treatment for 1h, filtering, putting a filtered substance into a high-temperature tube furnace, vacuumizing by a vacuum device, replacing argon, repeating for 3 times, and ensuring an oxygen-free environment; run the apparatus at 100sccm H2Mixed gas of/Ar (H)2The volume fraction of the silicon-carbon composite material is 5 percent), heating to 900 ℃ at the speed of 5 ℃/min, and preserving heat for 30min to obtain the silicon-carbon composite material.
The embodiment also provides a battery cathode material prepared from the silicon-carbon composite material and a lithium ion battery using the cathode material as the battery cathode material, and the preparation method comprises the following steps: mixing a silicon-carbon composite material, conductive carbon black and sodium alginate according to a ratio of 8:1:1 to prepare slurry, coating the slurry on a copper foil, drying the slurry for 2 hours at 70 ℃, cutting the slurry into pole pieces with the diameter of 12mm by using a slicing machine, taking a metal lithium foil as a counter electrode, taking an electrolyte as a 1M mixed solvent (the volume ratio of the front solvent to the rear solvent is 1:1) of ethylene carbonate and diethyl carbonate in which lithium hexafluorophosphate is dissolved, and assembling the diaphragm as Celgard 2400 to obtain the button type lithium ion battery.
The performance of the battery is tested, and the test result is as follows: at a current density of 0.5C, the gravimetric specific capacity is 1982 mAh/g; after 1000 cycles, the capacity retention was 90%.
Example 3
The embodiment provides a silicon-carbon composite material, which comprises a two-dimensional carbon nano material, a two-dimensional silicon nano material and a two-dimensional carbon nano material which are compounded from top to bottom in a face-to-face manner, wherein the mass percentage of silicon in the silicon-carbon composite material is 90%, the thickness of the two-dimensional silicon nano material is 5.4nm, and the length-diameter ratio of the two-dimensional silicon nano material is 20. The preparation method comprises the following steps: placing the two-dimensional silicon nano material prepared by a chemical oxidation stripping method into a high-temperature tube furnace, vacuumizing by a vacuum device, replacing argon, repeating for 3 times, and ensuring an oxygen-free environment; run the apparatus at 100sccm H2Mixed gas of/Ar (H)2The volume fraction of (1) is 5%), heating to 1100 deg.C at a rate of 5 deg.C/min, and introducing CH at a rate of 50sccm4And preserving the temperature for 10min, and depositing the graphene on the two-dimensional silicon nano material to obtain the silicon-carbon composite material.
The embodiment also provides a battery cathode material prepared from the silicon-carbon composite material and a lithium ion battery using the cathode material as the battery cathode material, and the preparation method comprises the following steps: mixing a silicon-carbon composite material, artificial graphite, conductive carbon black and sodium alginate according to a ratio of 1:7:1:1 to prepare slurry, coating the slurry on a copper foil, drying the slurry at 70 ℃ for 2 hours, cutting the slurry into pole pieces with the diameter of 12mm by a slicing machine, taking a metal lithium foil as a counter electrode, taking an electrolyte as 1M of a mixed solvent (the volume ratio of the front solvent to the rear solvent is 1:1) of ethylene carbonate and diethyl carbonate dissolved with lithium hexafluorophosphate, and assembling a diaphragm into a button type lithium ion battery, wherein the diaphragm is Celgard 2400.
The performance of the battery is tested, and the test result is as follows: the gravimetric specific capacity is 1988mAh/g at a current density of 0.5C; after 1000 cycles, the capacity retention rate was 96%.
Example 4
The embodiment provides a silicon-carbon composite material, which comprises a two-dimensional carbon nano material, a two-dimensional silicon nano material and a two-dimensional carbon nano material which are compounded from top to bottom in a face-to-face mode, wherein the mass percentage of silicon in the silicon-carbon composite material is 65%, the thickness of the two-dimensional silicon nano material is 6nm, and the length-diameter ratio of the two-dimensional silicon nano material is 15. The preparation method comprises the following steps: dispersing a two-dimensional silicon nano material prepared by a magnesiothermic reduction method in a 5% polyvinyl alcohol aqueous solution, adding graphene oxide, performing ultrasonic treatment for 1h, filtering, putting a filtered substance into a high-temperature tube furnace, vacuumizing by a vacuum device, replacing argon, repeating for 3 times, and ensuring an oxygen-free environment; run the apparatus at 100sccm H2Mixed gas of/Ar (H)295 percent), heating to 950 ℃ at the speed of 10 ℃/min, and preserving heat for 30min to obtain the silicon-carbon composite material.
The embodiment also provides a battery cathode material prepared from the silicon-carbon composite material and a lithium ion battery using the cathode material as the battery cathode material, and the preparation method comprises the following steps: mixing a silicon-carbon composite material, iron oxide, conductive carbon black and sodium alginate according to a ratio of 7:1:1:1 to prepare a slurry, coating the slurry on a copper foil, drying the slurry at 70 ℃ for 2 hours, cutting the slurry into pole pieces with the diameter of 12mm by a slicing machine, taking a metal lithium foil as a counter electrode, taking an electrolyte as 1M of a mixed solvent (the volume ratio of the front solvent to the rear solvent is 1:1) of ethylene carbonate and diethyl carbonate dissolved with lithium hexafluorophosphate, and assembling a diaphragm into a button type lithium ion battery, wherein the diaphragm is Celgard 2400.
The performance of the battery is tested, and the test result is as follows: the gravimetric specific capacity is 1563mAh/g under the current density of 0.5C; after 1000 cycles, the capacity retention was 90%.
Example 5
This example provides a silicon-carbon composite material, which is different from the silicon-carbon composite material in example 1 only in that "the mass percentage of silicon in the silicon-carbon composite material is 96%" is replaced with "the mass percentage of silicon in the silicon-carbon composite material is 30%" and the preparation method is the same.
The present embodiment also provides a battery negative electrode material made of the silicon-carbon composite material of this embodiment and a lithium ion battery using the negative electrode material as a battery negative electrode material, and the preparation method is also consistent with embodiment 1.
The performance of the battery is tested, and the test result is as follows: under the current density of 0.5C, the gravimetric specific capacity is 750 mAh/g; after 1000 cycles, the capacity retention rate was 96%.
Example 6
This example provides a silicon-carbon composite material, which is different from the silicon-carbon composite material in example 1 only in that "the mass percentage of silicon in the silicon-carbon composite material is 96%" is replaced with "the mass percentage of silicon in the silicon-carbon composite material is 99.5%" and the preparation method is the same.
The present embodiment also provides a battery negative electrode material made of the silicon-carbon composite material of this embodiment and a lithium ion battery using the negative electrode material as a battery negative electrode material, and the preparation method is also consistent with embodiment 1.
The performance of the battery is tested, and the test result is as follows: the gravimetric capacity is 2253mAh/g at a current density of 0.5C; after 1000 cycles, the capacity retention was 45%.
Example 7
This example provides a silicon-carbon composite material, which is different from the silicon-carbon composite material in example 1 only in that "the mass percentage of silicon in the silicon-carbon composite material is 96%" is replaced with "the mass percentage of silicon in the silicon-carbon composite material is 25%" and the preparation method is the same.
The present embodiment also provides a battery negative electrode material made of the silicon-carbon composite material of this embodiment and a lithium ion battery using the negative electrode material as a battery negative electrode material, and the preparation method is also consistent with embodiment 1.
The performance of the battery is tested, and the test result is as follows: the gravimetric specific capacity is 512mAh/g under the current density of 0.5C; after 1000 cycles, the capacity retention was 98%.
Example 8
This example provides a silicon-carbon composite material, which is different from the silicon-carbon composite material in example 1 only in that "the thickness of the two-dimensional silicon nanomaterial is 6 nm" is replaced with "the thickness of the two-dimensional silicon nanomaterial is 0.5 nm", and the preparation method thereof is also the same.
The present embodiment also provides a battery negative electrode material made of the silicon-carbon composite material of this embodiment and a lithium ion battery using the negative electrode material as a battery negative electrode material, and the preparation method is also consistent with embodiment 1.
The performance of the battery is tested, and the test result is as follows: under the current density of 0.5C, the gravimetric specific capacity is 2125 mAh/g; after 1000 cycles, the capacity retention was 90%.
Example 9
This example provides a silicon-carbon composite material, which is different from the silicon-carbon composite material in example 1 only in that "the thickness of the two-dimensional silicon nanomaterial is 6 nm" is replaced with "the thickness of the two-dimensional silicon nanomaterial is 1000 nm", and the preparation method thereof is also the same.
The present embodiment also provides a battery negative electrode material made of the silicon-carbon composite material of this embodiment and a lithium ion battery using the negative electrode material as a battery negative electrode material, and the preparation method is also consistent with embodiment 1.
The performance of the battery is tested, and the test result is as follows: under the current density of 0.5C, the gravimetric specific capacity is 2035 mAh/g; after 1000 cycles, the capacity retention was 75%.
Example 10
This example provides a silicon-carbon composite material, which is different from the silicon-carbon composite material in example 1 only in that "the thickness of the two-dimensional silicon nanomaterial is 6 nm" is replaced with "the thickness of the two-dimensional silicon nanomaterial is 1100 nm", and the preparation method thereof is also the same.
The present embodiment also provides a battery negative electrode material made of the silicon-carbon composite material of this embodiment and a lithium ion battery using the negative electrode material as a battery negative electrode material, and the preparation method is also consistent with embodiment 1.
The performance of the battery is tested, and the test result is as follows: at a current density of 0.5C, the gravimetric specific capacity is 2021 mAh/g; after 1000 cycles, the capacity retention was 43%.
Example 11
This example provides a silicon-carbon composite material, which is different from the silicon-carbon composite material in example 1 only in that "the thickness of the two-dimensional silicon nanomaterial is 6 nm" is replaced with "the thickness of the two-dimensional silicon nanomaterial is 0.4 nm", and the preparation method thereof is also the same.
The present embodiment also provides a battery negative electrode material made of the silicon-carbon composite material of this embodiment and a lithium ion battery using the negative electrode material as a battery negative electrode material, and the preparation method is also consistent with embodiment 1.
The performance of the battery is tested, and the test result is as follows: under the current density of 0.5C, the gravimetric specific capacity is 2121 mAh/g; after 1000 cycles, the capacity retention was 88%.
The results of the battery performance tests for examples 1-11 are summarized in Table 1:
TABLE 1
As can be seen from the data in Table 1: the silicon-carbon composite material has excellent electron/lithium ion transmission characteristics and structure/interface stability, and shows excellent charge-discharge specific capacity and cycling stability when used as a battery cathode material; comparing the data of example 1 and examples 5-7, it can be seen that: when the mass percentage of silicon in the silicon-carbon composite material is 30-99%, the silicon-carbon composite material shows better electron/lithium ion transmission characteristics and structure/interface stability; comparing the data of example 1 and examples 8-11, it can be seen that: the two-dimensional silicon nano material also shows better electron/lithium ion transmission characteristics and structure/interface stability when the thickness is 0.5-1000 nm.
The applicant states that the present invention is illustrated by the above examples to show the silicon carbon composite material of the present invention, the preparation method and the application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (10)
1. The silicon-carbon composite material is characterized by comprising a first two-dimensional carbon nano material layer, a two-dimensional silicon nano material layer and a second two-dimensional carbon nano material layer which are stacked from top to bottom.
2. The silicon-carbon composite material according to claim 1, wherein the silicon content in the silicon-carbon composite material is between 30 and 99% by weight, preferably between 50 and 80% by weight.
3. The silicon-carbon composite according to claim 1 or 2, wherein the thickness of the two-dimensional silicon nanomaterial layer is 0.5 to 1000nm, preferably 10 to 50 nm;
preferably, the ratio of the length of the short side of the two-dimensional silicon nanometer material layer to the thickness is 1-1000, preferably 10-100.
4. The silicon-carbon composite material according to any one of claims 1 to 3, wherein the surface of the two-dimensional silicon nanomaterial layer is modified with a carbonized and/or denatured dispersant;
preferably, the dispersant includes any one of or a combination of at least two of glucose, sucrose, fructose, maltose, chitosan, citric acid, urea, ascorbic acid, starch, protein, gelatin, gum arabic, alginate, cellulose, phenolic resin, polyvinylidene fluoride, polyamino acid, polyvinylpyrrolidone, polycarbonate, polyvinyl alcohol, polyethylene glycol, polymethyl methacrylate, polyethyl methacrylate, polyacrylic resin, polyvinyl chloride, polyacrylonitrile, polylactic acid, or polystyrene.
5. The silicon-carbon composite of any one of claims 1-4, wherein the two-dimensional carbon nanomaterial comprises any one of graphene, graphene oxide, reduced graphene oxide, or an amorphous two-dimensional carbon nanomaterial, or a combination of at least two thereof;
preferably, the amorphous two-dimensional carbon nanomaterial comprises a material obtained by carbonizing polyacrylic resin, polyvinyl chloride or polyacrylonitrile.
6. The method of preparing the silicon-carbon composite material of any one of claims 1 to 5, wherein the method comprises:
assembling a two-dimensional carbon nanomaterial on the upper and lower layers of a two-dimensional silicon nanomaterial layer by a chemical vapor deposition method or a chemical assembly method to obtain the silicon-carbon composite material;
preferably, the two-dimensional carbon nanomaterial is graphene, and the two-dimensional carbon nanomaterial is assembled on the upper and lower layers of the two-dimensional silicon nanomaterial layer by a chemical vapor deposition method;
preferably, the two-dimensional carbon nanomaterial is graphene oxide, reduced graphene oxide, or an amorphous two-dimensional carbon nanomaterial, and the two-dimensional carbon nanomaterial is assembled on the upper and lower layers of the two-dimensional silicon nanomaterial layer by a chemical assembly method.
7. The method according to claim 6, wherein the two-dimensional silicon nanomaterial is produced by a magnesiothermic reduction method, a chemical oxidation exfoliation method, or a physical vapor deposition method.
8. The method according to claim 6, wherein the atmosphere conditions of the chemical vapor deposition method include any one or a combination of at least two of nitrogen, argon, hydrogen, helium, or carbon dioxide;
preferably, the atmosphere condition of the chemical vapor deposition method is a mixed gas of hydrogen and argon;
preferably, H in the mixed gas2The concentration of (A) is 5% -95%;
preferably, the ventilation speed of the chemical vapor deposition method is 800-100 sccm;
preferably, the temperature rise speed of the chemical vapor deposition method is 5-10 ℃/min;
preferably, the deposition temperature of the chemical vapor deposition method is 900-1100 ℃;
preferably, the heat preservation time of the chemical vapor deposition method is 10-30 min;
preferably, the atmosphere conditions of the chemical assembling method include any one or a combination of at least two of nitrogen, argon, hydrogen, helium or carbon dioxide;
preferably, the atmosphere condition of the chemical assembling method is a mixed gas of hydrogen and argon;
preferably, H in the mixed gas2The concentration of (A) is 5% -95%;
preferably, the ventilation speed of the heat treatment of the chemical assembly method is 80-500 sccm;
preferably, the heating rate of the heat treatment of the chemical assembly method is 1-50 ℃/min;
preferably, the heat preservation temperature of the heat treatment of the chemical assembly method is 300-1200 ℃;
preferably, the heat preservation time of the heat treatment of the chemical assembly method is 5-600 min.
9. A battery negative electrode material, characterized in that the battery negative electrode material comprises the silicon-carbon composite material according to any one of claims 1 to 5;
preferably, the mass of the silicon-carbon composite material is not less than 1% of the total mass of the battery negative electrode material.
10. An electrochemical energy storage device comprising the silicon carbon composite of any one of claims 1-5;
preferably, the electrochemical energy storage device is a lithium ion battery.
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