CN114400327A - Preparation method of nano silicon-carbon negative electrode material - Google Patents
Preparation method of nano silicon-carbon negative electrode material Download PDFInfo
- Publication number
- CN114400327A CN114400327A CN202210012318.6A CN202210012318A CN114400327A CN 114400327 A CN114400327 A CN 114400327A CN 202210012318 A CN202210012318 A CN 202210012318A CN 114400327 A CN114400327 A CN 114400327A
- Authority
- CN
- China
- Prior art keywords
- carbon
- nano silicon
- nano
- silicon
- sio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
Abstract
The invention relates to a preparation method of a nano silicon-carbon cathode material, which is used for preparing nano SiO from tetraethoxysilane2Microspheres, nano SiO2Uniformly coating a polymer or organic matter layer on the surface of the microsphere to form a nano silicon-carbon precursor; under the protection of argon, the nano silicon-carbon precursor and magnesium powder are pyrolyzed, and the polymer on the surface of the nano silicon-carbon precursor is carbonized to form a coating on SiO2The carbon shell on the surface, the magnesium powder volatilizes into magnesium vapor, and the magnesium vapor permeates the carbon shell to enter the interior and the nanometerSiO2And reacting to obtain the nano silicon-carbon cathode material. Compared with the prior art, the nano silicon-carbon cathode material prepared by the invention is of a core-shell structure, silicon in the nano silicon-carbon cathode material is a core, the particle size of the silicon is all in a nano level, and the silicon is uniform in size and accounts for 5-60 wt%; the carbon layer is wrapped on the surface of the nano Si, and the carbon layer is used for protecting the nano Si, so that the capacity of the lithium ion battery is improved, and the cycle life of the lithium ion battery is prolonged.
Description
Technical Field
Hair brushThe invention relates to a material and a preparation method in the technical field of lithium batteries, in particular to a preparation method of a nano silicon carbon negative electrode material with uniform granularity, which relates to the preparation of nano SiO with uniform granularity through a magnesiothermic reduction reaction2The specific preparation process of the nano silicon-carbon cathode material.
Background
Lithium ion batteries have many advantages such as stable voltage, high energy density, long cycle life, etc. as an energy storage device, and thus are widely used in telephones, speakers, portable medical devices, electric motorcycles, electric automobiles, etc. The Chinese manufacture 2025 defines the development planning of power lithium batteries: in 2020, the energy density of the battery reaches 300 Wh/kg; in 2025, the energy density of the battery reaches 400 Wh/kg; therefore, development of a new anode material is urgently required. This puts higher demands on the negative electrode material of lithium batteries. The negative electrode material of the lithium ion battery at present is mainly carbon, the theoretical specific capacity is 372mAh/g, the capacity of the lithium ion battery sold in the market at present reaches more than 300mAh/g, the theoretical upper limit of the battery capacity of the carbon negative electrode material is approached, and the future development prospect of the lithium ion battery is limited. In addition, the lithium storage point of carbon is close to the precipitation potential of lithium, so that the lithium ion battery has explosion risk when being charged and discharged quickly. The silicon (Si) negative electrode material has the theoretical capacity as high as 4200mAh/g, is extremely wide in distribution in nature, has proper lithium embedding potential, and can greatly improve the capacity of the lithium battery if the silicon negative electrode material is adopted. But the silicon has large volume expansion coefficient, and can expand to 300 percent of the original volume to the maximum; after expansion, silicon can burst an SEI film and run off from a current collector, the service life of the lithium ion battery is greatly reduced, and the silicon has poor conductivity, so that the multiplying power performance of the silicon cathode is not high.
The Chinese patent CN 106374088 discloses a method for preparing a silicon-carbon composite material by a magnesiothermic reduction method for a lithium ion battery A, which mixes silicon dioxide with an organic carbon source, completes the reduction and high-temperature carbonization of the silicon dioxide by a one-step method, has low cost, can be produced in a large scale, and effectively keeps the shape of porous silicon. However, the patent adopts diatomite, mesoporous silica or quartz, and the particle size of the silica is large and cannot reach the nanometer level. In-process of productionLarge SiO particles in the preparation process2The silicon generated by reduction is easy to agglomerate, and the agglomerated silicon cannot avoid pulverization caused by silicon volume expansion and influence on the performance of the silicon-carbon negative electrode material.
Chinese patent CN 110350168A discloses a method for in-situ preparation of porous silicon-carbon composite material. The key point of the method is that 1, a polymer with positive charges and a solvent are mixed into a mixed solution; the key point 2 is to mix a silicon source and the mixed solution in the key point 1 to obtain a silicon-carbon precursor; the key point 3 is to mix the silicon-carbon precursor magnesium powder to obtain a crude product, and then to obtain the silicon-carbon composite material after acid washing. In the implementation process of the invention, because the magnesium powder and the silicon-carbon precursor are directly mixed, the magnesium powder can not be fully mixed with SiO in the process2And contacting to ensure that part of the silicon-carbon precursor can not completely react with magnesium in a reduction way to form the silicon-carbon composite material.
Chinese patent No. 103427073A discloses a preparation method of mesoporous Si/C composite microspheres used as a negative electrode of a lithium battery. The key point is that tetraethoxysilane, resorcinol and formaldehyde are mixed and reacted together, and are carbonized under the protection of the drying and at the temperature of 750 ℃ and 1000 ℃ to prepare SiO2the/C composite microspheres. Then SiO2And mixing the/C composite microspheres with magnesium powder, and reducing under the protection of argon to obtain the mesoporous Si/C composite microspheres. The reaction needs a two-step method to prepare the Si/C material, the working procedure is more complicated, the magnesium added in the formula is excessive, and SiO is required according to the patent2The reaction ratio with magnesium was 1: 2.5 magnesium powder is difficult to mix with SiO2The reaction occurs uniformly and a large amount of magnesium reacts with Si to form magnesium silicide, which affects the properties of the final product.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of a nano silicon-carbon negative electrode material.
The purpose of the invention can be realized by the following technical scheme: the preparation method of the nano silicon-carbon cathode material is characterized in that nano SiO is prepared from tetraethoxysilane2Micro-sphere, nanoSiO rice2Uniformly coating a polymer or organic matter layer on the surface of the microsphere to form a nano silicon-carbon precursor; under the protection of argon, the nano silicon-carbon precursor and magnesium powder are pyrolyzed, and the polymer on the surface of the nano silicon-carbon precursor is carbonized to form a coating on SiO2The carbon shell on the surface, the magnesium powder volatilizes into magnesium vapor, and the magnesium vapor permeates the carbon shell to enter the interior and the nano SiO2And reacting to obtain the nano silicon-carbon cathode material.
Further, the nano SiO2The diameter range of the microspheres is 80nm-800 nm.
Further, the nano SiO2The microspheres are prepared by the following method: the ethyl orthosilicate is reacted with ammonia water, sodium hydroxide, potassium hydroxide, oxalic acid, dilute hydrochloric acid or citric acid to prepare the catalyst.
Further, the nano silicon-carbon precursor is prepared by the following method:
mixing nano SiO2Dispersing the microspheres in the solution, adding polymer monomer and initiator, stirring at 40-90 deg.C to coat the organic matter on the SiO nanoparticles2Forming a microsphere surface containing nano SiO2Drying the polymer microsphere solution to obtain the nano silicon-carbon precursor. The nano SiO2The dosage ratio of the microspheres to the polymer monomer and the initiator is 9: 0.9: 0.1-6: 2.5: 0.5.
further, the polymer monomer is one or more of styrene, acrylonitrile, methacrylic acid, methyl methacrylate, aromatic carbonate, diamine, dibasic acid, phenol or formaldehyde;
further, the initiator is one or more of potassium persulfate, benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile or azobisisoheptane;
further, the solvent is benzene, toluene, dimethylformamide or water.
Further, the nano silicon-carbon precursor is prepared by the following method:
dissolving polymer or organic matter in solvent to obtain nano SiO2Adding the microspheres into the solution, and stirring orUltrasonic vibration mode for making nano SiO2The microspheres are uniformly dispersed in the solution to prepare a polymer microsphere solution, and the polymer microsphere solution is dried to obtain the nano silicon-carbon precursor. The nano SiO2The dosage ratio of the microspheres to the polymer or organic matter is 9: 0.9: 0.1-6: 2.5: 0.5.
further, the polymer or organic matter is one or more of polystyrene, polyacrylonitrile, polymethacrylic acid, polymethyl methacrylate, polypyrrole, polyamide, polyimide, polyvinyl alcohol, polyvinyl acetate, polycarbonate, phenolic resin, epoxy resin, glucose, sucrose, chitin, starch and lignin;
further, the solvent is benzene, toluene, dimethylformamide or water.
Further, the drying is to dry the polymer microsphere solution and then perform ball milling and crushing, or freeze drying or spray drying to obtain particles, and then the particles are screened by a 400-mesh screen to form the nano silicon-carbon precursor.
Further, the pyrolysis is to place the nano silicon-carbon precursor and magnesium powder in a crucible, separately place the crucible and the magnesium powder, place the crucible and the magnesium powder in an electric furnace, heat the crucible to 650-1000 ℃ under the protection of argon or the mixed atmosphere of argon and hydrogen, preserve the temperature for 2-6h, and then cool the crucible and the magnesium powder to obtain the nano silicon-carbon material containing impurities. The dosage ratio of the nano silicon-carbon precursor to the magnesium powder is 9: 1-7: 3.
and washing the nano silicon-carbon material containing impurities with deionized water, pickling and filtering to obtain the nano silicon-carbon material.
Compared with the prior art, the invention has the following beneficial effects:
1) the method adopts a one-step method to generate the nano silicon-carbon cathode material, and has simple process and low cost.
2) The grain diameter of silicon in the nano silicon-carbon cathode material prepared by the invention is all in nano level, and the nano silicon has special size effect, so that the pulverization phenomenon caused by volume expansion when the silicon is used as the cathode of the lithium ion battery can be reduced, and the attenuation of the battery capacity can be reduced.
3) The nano silicon-carbon cathode material prepared by the invention has uniform silicon size of 30-500nm,
4) the silicon content in the nano silicon-carbon cathode material prepared by the invention can be adjusted, and can be from 5 wt% to 50 wt%.
5) The nano silicon carbon cathode material is coated with a carbon layer outside nano silicon, so that the agglomeration among the nano silicon is avoided.
6) The carbon layer of the nano silicon carbon negative electrode material limits the expansion of nano silicon, and can reduce the capacity attenuation of the lithium ion battery caused by pulverization loss in the charging and discharging processes of the lithium ion battery.
Drawings
FIG. 1 is a scanning electron micrograph of the nano-silicon-carbon negative electrode obtained in example 1;
FIG. 2 is a charge-discharge curve of the nano-Si-C negative electrode obtained in example 1;
FIG. 3 is the rate capability of the nano-silicon carbon anode obtained in example 1;
FIG. 4 is the charge and discharge curve of the nano-Si-C negative electrode obtained in example 2;
fig. 5 shows rate capability of nano silicon carbon negative electrode obtained in example 2.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The invention can be realized by the following technical scheme, comprising the following steps:
(1) preparing organic matter coated nano SiO with uniform granularity2Particles;
(1-1) mixing ethyl orthosilicate and ammonia water according to a mass ratio of 8: 2-1: 9 mixing, stirring and reacting at the constant temperature of 28 ℃ to prepare nano SiO with uniform granularity2Washing with ethanol and deionized water for several times;
(1-2) subjecting the above-mentioned nano SiO2Dispersed in a solution, and since the dispersion is made in a solvent,ultrasonic vibration is used for preparing nano SiO2Can be fully dispersed without agglomeration, polymer monomer, initiator and the like are added, and organic matters are uniformly coated on the nano SiO by solution or emulsion polymerization at a certain temperature and stirring speed2The surface of the particles is formed to contain nano SiO2The polymer microsphere solution of (1). Or dissolving polymer or organic matter in some solvent to obtain nanometer SiO2Is added to the solution. Then stirring or ultrasonic vibrating the nano SiO2Uniformly dispersing the polymer microspheres in the solution, and preparing the polymer microsphere solution.
(2) Preparing a nano silicon-carbon negative electrode material;
(2-1) coating the organic substance prepared in the above (1) with nano SiO2Preparing a nano silicon-carbon precursor by spray drying, or drying at a certain temperature and then processing by a ball mill or a powder crusher, or freeze drying, then respectively placing the precursor and magnesium powder in a crucible according to a certain proportion, introducing argon or argon/hydrogen, and placing the precursor in a muffle furnace. After the temperature is raised, the crucible is fully heated, the polymer on the surface of the nano silicon-carbon precursor is carbonized to form a carbon shell, magnesium powder is volatilized to form magnesium vapor, and the magnesium vapor permeates into the carbon layer and SiO in the carbon layer when penetrating through the nano silicon-carbon precursor2Reacting to generate nano silicon, and cooling to obtain a mixture containing nano silicon and carbon;
and (2-2) respectively cleaning the nano silicon-carbon mixture by using deionized water, dilute hydrochloric acid or sulfuric acid and hydrofluoric acid to remove impurities, thereby obtaining nano silicon-carbon particles.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
Example 1
Mixing ethyl orthosilicate and ammonia water according to a mass ratio of 8: 2, mixing, and reacting at the constant temperature of 28 ℃ to obtain the nano SiO2To obtain the product containing nano SiO2Washing the microsphere solution, and taking the solution containing 1g of nano SiO2Dispersing the solution in 170ml deionized water, performing ultrasonic dispersion for 10min, adding 10.5mg of styrene monomer and 0.35mg of methacrylic acid, performing electromagnetic stirring, fully mixing, and performing water bathHeating to 80 ℃, keeping the temperature constant for 30min, adding 0.037mg of potassium persulfate, stirring at a constant speed under the protection of nitrogen, reacting at the constant temperature of 80 ℃ for 10h, and then cooling to room temperature to obtain the polymer microsphere with the nano Si as the core. Washing with deionized water, vacuum filtering, and drying in oven at 50 deg.C for 12 hr. Grinding and sieving with a 400-mesh sieve to obtain coated nano SiO2And (3) granulating to obtain a nano silicon-carbon precursor, respectively filling the nano silicon-carbon precursor and 0.8g of magnesium powder into a crucible, then placing the crucible into an electric furnace, heating to 700 ℃ at a heating rate of 5 ℃/min under the protection of argon, keeping the temperature for 4 hours, cooling and then taking out. Washing the silicon-carbon nano-anode material once by using 100ml of deionized water, then washing the silicon-carbon nano-anode material by using 100ml of 5% HCl and 1% HF, and drying the silicon-carbon nano-anode material to obtain the nano-silicon-carbon nano-anode material, wherein a scanning electron microscope picture of the nano-silicon-carbon nano-anode material is shown in figure 1.
FIG. 2 is the charge-discharge curve of the nano-Si-C negative electrode obtained in example 1, and it can be seen that the nano-Si-C negative electrode has a specific discharge capacity as high as 2450 mAh/g.
Fig. 3 shows the rate capability of the nano silicon-carbon negative electrode obtained in example 1, and it can be seen that the nano silicon-carbon negative electrode has excellent rate capability, and the specific discharge capacities at 2C and 5C discharge currents are 1320mAh/g and 940 mAh/g, respectively.
Example 2
Mixing ethyl orthosilicate and ammonia water according to the proportion of 7: 3, reacting at the constant temperature of 28 ℃ to obtain the nano SiO2To obtain the product containing nano SiO2Washing the microsphere solution, and taking the microsphere solution containing 2g of nano SiO2The solution is ultrasonically dispersed for 10min, 10.5mg of styrene monomer and 0.35mg of methacrylic acid are added, the mixture is fully mixed by electromagnetic stirring, the mixture is heated in a water bath at 80 ℃, 0.040mg of potassium persulfate is added after the constant temperature is kept for 30min, the mixture is uniformly stirred under the protection of nitrogen, the mixture is reacted at the constant temperature of 80 ℃ for 10h, the mixture is cooled to the room temperature, and the coated nano SiO is obtained after freeze drying2And (3) passing the microspheres through a 400-mesh screen to obtain the nano silicon-carbon precursor. And respectively filling the nano silicon-carbon precursor and 1.6g of magnesium powder into a crucible, then placing the crucible into an electric furnace, heating to 800 ℃ at a heating rate of 10 ℃/min under the protection of argon, keeping the temperature for 3 hours, cooling and then taking out. Use 100ml to removeWashing with ionic water once, then washing with 100ml of 5% HCl and 1% HF, and drying to obtain the nano silicon-carbon negative electrode material. Fig. 4 is a charge-discharge curve of the nano silicon-carbon negative electrode obtained in example 2, and it can be seen that the nano silicon-carbon negative electrode has a specific discharge capacity as high as 2300 mAh/g.
Fig. 5 shows the rate capability of the nano silicon-carbon negative electrode obtained in example 2, and it can be seen that the nano silicon-carbon negative electrode has excellent rate capability, and the specific discharge capacities under 2C and 5C discharge currents are 1410mAh/g and 1020 mAh/g, respectively.
Example 3
Mixing ethyl orthosilicate and ammonia water according to the proportion of 6: 4 proportion, and reacting at the constant temperature of 28 ℃ to obtain the nano SiO2To obtain the product containing nano SiO2Washing the microsphere solution, taking a solution containing 4g of nano SiO2, and adding 0.4g of glucose to obtain a uniformly dispersed mixed solution; drying the mixed solution at 105 deg.C for 24 hr, removing water to obtain dry glucose-coated nanometer SiO2And (3) granules. Crushing by a ball mill, and sieving by a 400-mesh sieve to obtain the glucose-coated nano SiO2And (5) carrying out microsphere preparation to obtain the nano silicon-carbon precursor. And respectively filling SiO2 and 3.2g of magnesium powder in the particles into a crucible, then placing the crucible into an electric furnace, heating to 850 ℃ at a heating rate of 15 ℃/min under the protection of argon, keeping the temperature for 2 hours, cooling and then taking out. And obtaining the nano silicon-carbon cathode material.
Example 4
Mixing ethyl orthosilicate and ammonia water according to the proportion of 5: 5 proportion, reacting at 28 deg.C to obtain self-assembled nanometer SiO2To obtain the product containing nano SiO2Washing the microsphere solution, and taking the microsphere solution containing 4g of nano SiO2Adding 0.2g of glucose into the solution to obtain a uniformly dispersed mixed solution; drying the mixed solution at 105 deg.C for 24 hr, removing water to obtain dry glucose-coated nanometer SiO2And (3) granules. And spray drying to obtain the glucose-coated nano silicon-carbon precursor. And respectively placing the nano silicon-carbon precursor and 3.2g of magnesium powder in a crucible, placing the crucible in an electric furnace, heating to 900 ℃ at a heating rate of 15 ℃/min under the protection of argon, keeping the temperature for 2 hours, cooling and taking out. And obtaining the nano silicon-carbon cathode material.
The nano silicon carbon negative electrode materials obtained in the above examples 1 to 4 are used as a negative electrode of a lithium sulfur battery, an electrode active material, a conductive agent and a binder are mixed and ground according to the mass ratio of 80%, 10% and 10%, a proper amount of N-methyl pyrrolidone solution is added, ultrasonic stirring is carried out to obtain slurry, then the slurry is coated on a copper foil to obtain a lithium selenium battery positive electrode sheet, and the lithium sheet is used as a counter electrode to assemble the battery.
The lithium battery assembled by the method is subjected to performance detection, and the detection method comprises the following steps:
specific capacity: and (3) placing the assembled battery on a battery tester, setting a charging and discharging voltage interval and constant current parameters, testing the battery capacity in a constant current charging and discharging mode, and calculating the specific capacity of the battery according to the quality of the electrode active material.
Energy density: and placing the assembled battery on a battery tester, setting a charging and discharging voltage interval and constant current parameters, testing the energy of the battery in a constant current charging and discharging mode, and calculating the energy density according to the mass of the battery.
Electron conductivity: the assembled cell was placed on an electrochemical workstation, the frequency was set, and the electrochemical impedance of the cell was tested. And performing equivalent circuit fitting on the impedance to obtain each partial resistance, thereby judging the electron conductivity.
Ion transmission rate: and (3) placing the assembled battery on an electrochemical workstation, setting a voltage interval and a voltage sweeping speed, and testing cyclic voltammetry curves of the battery at different sweeping speeds. And calculating the ion transmission rate of the battery according to the cyclic voltammetry curve result.
Rate capability: and placing the assembled battery on a battery tester, setting a charging and discharging voltage interval, setting gradually-increased current parameters, and obtaining the multiplying power performance of the battery according to the charging and discharging capacity and the electrode active material quality under different charging and discharging currents.
In the comparative example, silica-source diatomite (i.e., commercially available diatomite with a general particle size of 10-100 microns) with coarse particles and an organic source (styrene monomer) are mixed and reduced by the same method as in example 1 to obtain a carbon-silicon composite material, and the lithium battery in the comparative example is prepared, and the detection results are shown in the following table:
as can be seen from the above table, the comparative example using the silica source diatomaceous earth having coarse particles does not produce the nano effect, and the battery performance is far inferior to that of the present invention.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The preparation method of the nano silicon-carbon cathode material is characterized in that nano SiO is prepared from tetraethoxysilane2Microspheres, nano SiO2Uniformly coating a polymer or organic matter layer on the surface of the microsphere to form a nano silicon-carbon precursor; under the protection of argon, the nano silicon-carbon precursor and magnesium powder are pyrolyzed before nano silicon-carbonThe polymer on the surface of the driver is carbonized to form a coating on SiO2The carbon shell on the surface, the magnesium powder volatilizes into magnesium vapor, and the magnesium vapor permeates the carbon shell to enter the interior and the nano SiO2And reacting to obtain the nano silicon-carbon cathode material.
2. The method for preparing nano silicon carbon anode material according to claim 1, wherein the nano SiO is2The diameter range of the microspheres is 80nm-800 nm.
3. The method for preparing nano silicon carbon anode material according to claim 1 or 2, wherein the nano SiO is2The microspheres are prepared by the following method: the ethyl orthosilicate is reacted with ammonia water, sodium hydroxide, potassium hydroxide, oxalic acid, dilute hydrochloric acid or citric acid to prepare the catalyst.
4. The method for preparing the nano silicon-carbon anode material according to claim 1, wherein the nano silicon-carbon precursor is prepared by the following steps:
mixing nano SiO2Dispersing the microspheres in the solution, adding polymer monomer and initiator, stirring at 40-90 deg.C to coat the organic matter on the SiO nanoparticles2Forming a microsphere surface containing nano SiO2Drying the polymer microsphere solution to obtain the nano silicon-carbon precursor.
5. The preparation method of the nano silicon-carbon anode material as claimed in claim 4, wherein the polymer monomer is one or more of styrene, acrylonitrile, methacrylic acid, methyl methacrylate, aromatic carbonate, diamine, dibasic acid, phenol or formaldehyde;
the initiator is one or more of potassium persulfate, benzoyl peroxide, lauroyl peroxide, azodiisobutyronitrile or azodiisoheptylene;
the solvent is benzene, toluene, dimethylformamide or water.
6. The method for preparing the nano silicon-carbon anode material according to claim 1, wherein the nano silicon-carbon precursor is prepared by the following steps:
dissolving polymer or organic matter in solvent to obtain nano SiO2Adding the microspheres into the solution, and stirring or ultrasonically vibrating to obtain nanometer SiO2The microspheres are uniformly dispersed in the solution to prepare a polymer microsphere solution, and the polymer microsphere solution is dried to obtain the nano silicon-carbon precursor.
7. The method for preparing the nano silicon-carbon negative electrode material according to claim 6, wherein the polymer or organic matter is one or more of polystyrene, polyacrylonitrile, polymethacrylic acid, polymethyl methacrylate, polypyrrole, polyamide, polyimide, polyvinyl alcohol, polyvinyl acetate, polycarbonate, phenolic resin, epoxy resin, glucose, sucrose, chitin, starch and lignin;
the solvent is benzene, toluene, dimethylformamide or water.
8. The preparation method of the nano silicon-carbon anode material according to claim 4 or 6, wherein the drying is to dry the polymer microsphere solution and then ball mill and crush the dried polymer microsphere solution, or freeze-dry the dried polymer microsphere solution or spray-dry the dried polymer microsphere solution to obtain particles, and the particles are screened by a 400-mesh screen to form a nano silicon-carbon precursor.
9. The method for preparing nano silicon-carbon anode material according to claim 1, wherein the pyrolysis is to place the nano silicon-carbon precursor and magnesium powder in a crucible, separately place them, place them in an electric furnace, heat them to 650-1000 ℃ under the protection of argon or the mixed atmosphere of argon and hydrogen, preserve heat for 2-6h, and then cool them to obtain the nano silicon-carbon material containing impurities.
10. The method for preparing nano silicon-carbon anode material according to claim 9, wherein the nano silicon-carbon material containing impurities is washed with deionized water, acid-washed, and filtered to obtain the nano silicon-carbon material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210012318.6A CN114400327A (en) | 2022-01-07 | 2022-01-07 | Preparation method of nano silicon-carbon negative electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210012318.6A CN114400327A (en) | 2022-01-07 | 2022-01-07 | Preparation method of nano silicon-carbon negative electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114400327A true CN114400327A (en) | 2022-04-26 |
Family
ID=81229315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210012318.6A Pending CN114400327A (en) | 2022-01-07 | 2022-01-07 | Preparation method of nano silicon-carbon negative electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114400327A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114914430A (en) * | 2022-06-10 | 2022-08-16 | 蜂巢能源科技股份有限公司 | Silicon negative electrode material, preparation method thereof and lithium ion battery |
| CN116969464A (en) * | 2023-09-22 | 2023-10-31 | 中石油深圳新能源研究院有限公司 | Lithium ion battery negative electrode material and preparation method thereof |
| CN117199378A (en) * | 2023-11-06 | 2023-12-08 | 浙江吉利控股集团有限公司 | Silicon-based negative electrode material and lithium ion battery |
| CN117476902A (en) * | 2023-11-24 | 2024-01-30 | 湖北美赛尔科技有限公司 | Silicon-based negative electrode material with ultralow temperature and high cycle stability and lithium ion battery thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102867944A (en) * | 2011-07-06 | 2013-01-09 | 东丽纤维研究所（中国）有限公司 | Mesoporous carbon/silicon composite anode material and preparation method thereof |
| CN103427073A (en) * | 2013-08-05 | 2013-12-04 | 同济大学 | Preparation method of mesoporous Si/C composite microsphere as lithium battery negative electrode material |
| CN103682272A (en) * | 2013-12-11 | 2014-03-26 | 上海交通大学 | Lithium ion battery cathode material and preparation method thereof |
| CN104466185A (en) * | 2014-11-12 | 2015-03-25 | 中国科学院深圳先进技术研究院 | Silicon/carbon negative electrode composite material and preparation method thereof as well as lithium ion battery and negative electrode thereof |
| CN106374088A (en) * | 2016-10-14 | 2017-02-01 | 浙江天能能源科技股份有限公司 | Method for preparing silicon/carbon composite material with magnesiothermic reduction process |
| CN107611415A (en) * | 2017-08-04 | 2018-01-19 | 西南石油大学 | A kind of preparation method of the spherical porous silicium cathode material of lithium ion battery |
| CN109244401A (en) * | 2018-09-04 | 2019-01-18 | 南京工业大学 | A kind of porous nano Si-C composite material and preparation method thereof using magnesium reduction process preparation |
| CN111446432A (en) * | 2020-04-20 | 2020-07-24 | 上海交通大学 | Preparation method of nano silicon/carbon composite negative electrode material for lithium ion battery |
| JP2021068665A (en) * | 2019-10-28 | 2021-04-30 | 東ソー株式会社 | Composite material with core-shell structure, manufacturing method thereof, and negative electrode material |
-
2022
- 2022-01-07 CN CN202210012318.6A patent/CN114400327A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102867944A (en) * | 2011-07-06 | 2013-01-09 | 东丽纤维研究所（中国）有限公司 | Mesoporous carbon/silicon composite anode material and preparation method thereof |
| CN103427073A (en) * | 2013-08-05 | 2013-12-04 | 同济大学 | Preparation method of mesoporous Si/C composite microsphere as lithium battery negative electrode material |
| CN103682272A (en) * | 2013-12-11 | 2014-03-26 | 上海交通大学 | Lithium ion battery cathode material and preparation method thereof |
| CN104466185A (en) * | 2014-11-12 | 2015-03-25 | 中国科学院深圳先进技术研究院 | Silicon/carbon negative electrode composite material and preparation method thereof as well as lithium ion battery and negative electrode thereof |
| CN106374088A (en) * | 2016-10-14 | 2017-02-01 | 浙江天能能源科技股份有限公司 | Method for preparing silicon/carbon composite material with magnesiothermic reduction process |
| CN107611415A (en) * | 2017-08-04 | 2018-01-19 | 西南石油大学 | A kind of preparation method of the spherical porous silicium cathode material of lithium ion battery |
| CN109244401A (en) * | 2018-09-04 | 2019-01-18 | 南京工业大学 | A kind of porous nano Si-C composite material and preparation method thereof using magnesium reduction process preparation |
| JP2021068665A (en) * | 2019-10-28 | 2021-04-30 | 東ソー株式会社 | Composite material with core-shell structure, manufacturing method thereof, and negative electrode material |
| CN111446432A (en) * | 2020-04-20 | 2020-07-24 | 上海交通大学 | Preparation method of nano silicon/carbon composite negative electrode material for lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| XIANGZHONG KONG等: "Necklace-like Si@C nanofibers as robust anode materials for high performance lithium ion batteries", 《SCIENCE BULLETIN》, vol. 64, no. 4, pages 261 - 269 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114914430A (en) * | 2022-06-10 | 2022-08-16 | 蜂巢能源科技股份有限公司 | Silicon negative electrode material, preparation method thereof and lithium ion battery |
| CN116969464A (en) * | 2023-09-22 | 2023-10-31 | 中石油深圳新能源研究院有限公司 | Lithium ion battery negative electrode material and preparation method thereof |
| CN117199378A (en) * | 2023-11-06 | 2023-12-08 | 浙江吉利控股集团有限公司 | Silicon-based negative electrode material and lithium ion battery |
| CN117199378B (en) * | 2023-11-06 | 2024-03-12 | 浙江吉利控股集团有限公司 | Silicon-based negative electrode material and lithium ion battery |
| CN117476902A (en) * | 2023-11-24 | 2024-01-30 | 湖北美赛尔科技有限公司 | Silicon-based negative electrode material with ultralow temperature and high cycle stability and lithium ion battery thereof |
| CN117476902B (en) * | 2023-11-24 | 2024-04-02 | 湖北美赛尔科技有限公司 | Silicon-based negative electrode material with ultralow temperature and high cycle stability and lithium ion battery thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114400327A (en) | Preparation method of nano silicon-carbon negative electrode material | |
| CN107785560B (en) | High-performance silicon-carbon negative electrode material and preparation method thereof | |
| CN106711461A (en) | Spherical porous silicon/carbon composite material as well as preparation method and application thereof | |
| WO2022121137A1 (en) | One-dimensional porous silicon-carbon composite negative electrode material, preparation method, and application thereof | |
| CN107634207B (en) | Silicon-inlaid redox graphene/graphite-phase carbon nitride composite material and preparation and application thereof | |
| CN106848264A (en) | A kind of porous silicon oxide lithium ion battery negative material and preparation method thereof | |
| CN112018334A (en) | Silicon oxide/carbon composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN107026262B (en) | High-capacity spherical hard carbon negative electrode material coated with graphene on surface | |
| CN111446432A (en) | Preparation method of nano silicon/carbon composite negative electrode material for lithium ion battery | |
| CN106784741B (en) | Carbon-silicon composite material, preparation method thereof and lithium ion battery containing composite material | |
| WO2013010346A1 (en) | Lithium-ion battery negative electrode-use silicon-carbon composite material and preparation method therefor | |
| CN105226254B (en) | A kind of silicon nanoparticle graphite nano plate carbon fibre composite and preparation method and application | |
| CN110350161B (en) | Preparation method of silicon-carbon negative electrode precursor | |
| CN110797512A (en) | Silicon-carbon negative electrode material, lithium ion battery negative electrode and lithium ion battery | |
| CN113690427A (en) | Preparation method of lithium-silicon alloy pole piece, lithium-silicon alloy pole piece and lithium battery | |
| CN114267493B (en) | Nitrogen-doped graphene-based aqueous conductive paste and preparation method and application thereof | |
| CN115332523B (en) | Silicon-carbon negative electrode material derived by using polymer gel as matrix and preparation method thereof | |
| CN110098402B (en) | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof | |
| CN114050243B (en) | Nitrogen-doped synergic conductive polymer modified silicon-carbon composite anode material and preparation method thereof | |
| CN115050932A (en) | Composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN108807903B (en) | Preparation method of composite modified lithium battery negative electrode material for lithium battery | |
| CN113644243A (en) | Nitrogen-doped hollow-structure graphite microsphere, composite negative electrode material and preparation method of composite negative electrode material | |
| CN113471419A (en) | Silicon-carbon composite material and preparation method and application thereof | |
| CN112520732A (en) | Silicon-carbon composite negative electrode material and preparation method thereof | |
| CN112520719A (en) | Polyimide modified carbon-silicon negative electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |