CN111416114A - Nano hollow Si @ C @ SiO2@ C multilayer structure composite microsphere and preparation method and application thereof - Google Patents

Nano hollow Si @ C @ SiO2@ C multilayer structure composite microsphere and preparation method and application thereof Download PDF

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CN111416114A
CN111416114A CN202010328877.9A CN202010328877A CN111416114A CN 111416114 A CN111416114 A CN 111416114A CN 202010328877 A CN202010328877 A CN 202010328877A CN 111416114 A CN111416114 A CN 111416114A
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calcium carbonate
microspheres
multilayer structure
hollow
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王杰
刘风光
韩勇
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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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Nano hollow Si @ C @ SiO2The preparation method of the @ C multilayer structure composite microsphere is realized by the following steps: calcium carbonate microspheres are used as a template, a silicon source is used for hydrolyzing the surface of the calcium carbonate microspheres and wrapping the calcium carbonate microspheres to form calcium carbonate @ SiO2(ii) a Calcium carbonate @ SiO2Putting the microspheres into high-concentration polymer solution, and coating a layer of polymer material on the surfaces of the microspheres to form calcium carbonate @ SiO2@ macromolecular compound; calcium carbonate @ SiO2@ high scoreTransferring the product to a high-temperature atmosphere furnace, performing high-temperature sintering at 800-1200 ℃ in a hydrogen-argon mixed atmosphere, transferring the product to an acid solution, and further washing to remove impurities to obtain the hollow Si @ C composite structure material; respectively coating the hollow Si @ C composite structure material with SiO2And treating the layer and the oligomer layer under the hydrothermal condition of 160-200 ℃, and after the reaction is finished, washing the product with water to obtain the multilayer structure composite microsphere.

Description

Nano hollow Si @ C @ SiO2@ C multilayer structure composite microsphere and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a nano hollow Si @ C @ SiO2@ C multilayer structure composite microBall and its preparation method and application.
Background
The lithium ion battery has good safety, economy and stability. In recent years, the battery pack has been widely used in the fields of mobile phones, computers, power batteries and the like. However, the conventional lithium ion battery has a low energy density limit, so that the improvement of the simple graphite-based negative electrode material is urgently needed. For the improvement strategy, the currently studied method is to carry out compounding, for example, silicon-carbon composite materials represented by silicon element show better application prospect.
Specifically, chinese patent CN108899484A discloses a method for preparing a carbon-coated hollow silicon tube as a negative electrode material of a lithium ion battery, which comprises the following steps: preparing a zinc oxide nanorod, adding sodium alginate into a zinc acetate solution, adding ammonia water to adjust the pH, and performing hydrothermal reaction to obtain the nanorod zinc oxide; coating a silicon dioxide layer on the surface of the zinc oxide by utilizing the hydrolysis action of tetraethoxysilane, and dissolving the zinc oxide by using acid; coating a carbon layer on the surface of silicon dioxide by using acetylene as a carbon source through a chemical vapor deposition method, and reducing the silicon dioxide into monocrystalline silicon through a magnesiothermic reduction method to obtain the carbon-coated hollow silicon tube. For example, CN106450192A discloses a silicon-carbon composite material for lithium ion batteries, and a preparation method and an application thereof, and belongs to the field of materials science. The preparation method comprises the following steps: firstly, silicon powder and a template agent are filled in a carbon precursor, the template agent is dissolved after the carbon is pyrolyzed, and a large number of holes are left in the carbon precursor, so that the silicon is uniformly dispersed in the porous carbon matrix. CN105006549A discloses a carbon-silicon composite lithium ion battery cathode material and a preparation method thereof, wherein Si is used as a core, and the outer surface of the Si is tightly coated with a layer of SiO2Layer of SiO2The hollow layer is arranged between the layer and the outermost layer C cladding layer, the mass percentage of the inner core Si in the composite material is 30-70%, and the composite material is published in 2016 by Xuelian university Xuelian L iu2The @ Chollow sphere elastomers for lithium-ion batteries uses template agent, then coats a layer of silicon oxide on the template agent, coats a layer of high molecular material after passing through a template agent, and finally carries out high-temperature pyrolysis treatmentCarbonizing the high molecular material into a carbon coating layer to obtain hollow SiO2@ C hollow sphere.
In addition, there is a need for similar work to study the structure of silicon carbon composites and their properties. However, the above documents do not solve the cycling stability and specific capacity of the silicon-carbon composite material well, which is far from the theoretical capacity of silicon.
Disclosure of Invention
The invention discloses a nano hollow Si @ C @ SiO2The target product prepared by the method has a nano structure, a hollow structure is introduced, a multi-layer surface composite structure is adopted, and the prepared silicon-carbon composite material is applied to a lithium ion battery cathode.
The specific technical scheme is as follows:
nano hollow Si @ C @ SiO2The preparation method of the @ C multilayer structure composite microsphere comprises the following steps:
step 1: calcium carbonate microspheres are used as a template, a silicon source is used for hydrolyzing the surface of the calcium carbonate microspheres and wrapping the calcium carbonate microspheres to form calcium carbonate @ SiO2；
Step 2: calcium carbonate @ SiO obtained in step 12Putting the microspheres into high-concentration polymer solution, and coating a layer of polymer material on the surfaces of the microspheres to form calcium carbonate @ SiO2@ macromolecular compound;
and step 3: calcium carbonate @ SiO in step 22The @ polymer is transferred into a high-temperature atmosphere furnace and is sintered at high temperature of 800-1200 ℃ in a hydrogen-argon mixed atmosphere;
and 4, step 4: transferring the high-temperature sintering product obtained in the step 3 into an acidic solution, and further washing and removing impurities to obtain a hollow Si @ C composite structure material;
and 5: respectively coating the hollow Si @ C composite structure material obtained in the step 4 with SiO2The layer and the oligomer layer are treated under the hydrothermal condition of 160-200 ℃, and after the reaction is finished, the product is washed by water to obtain the target product nano hollow Si @ C @ SiO2@ C duoThe layer structure composite microsphere.
Preferably, the silicon source in the present invention is one selected from TEOS and sodium silicate.
Preferably, the polymer in the present invention is one of PVA, PVP and PS.
Preferably, the acidic solution in the present invention refers to one of hydrochloric acid, nitric acid or sulfuric acid.
Preferably, the oligomer in the present invention refers to one of glucose, sucrose or fructose.
Preferably, the hydrothermal treatment time in the invention is 16-28 h.
Preferably, the silicon source in the present invention is hydrolyzed on the surface of calcium carbonate, specifically by the following steps:
uniformly mixing deionized water, ammonia water and absolute ethyl alcohol, and then uniformly mixing the absolute ethyl alcohol and TEOS; slowly adding the latter solution into the former solution, stirring at room temperature for reaction, washing, and drying to obtain the calcium carbonate compound wrapped with silicon oxide.
Preferably, the volume ratio of the deionized water to the ammonia water to the absolute ethyl alcohol is 5-8: 1-2: 80-90; the volume ratio of the absolute ethyl alcohol to the TEOS is 20-30: 1.
In this step, the above-mentioned parameter ratios are interrelated, and any deviation from the above-mentioned ratios will not result in a uniform coating, or even if a uniform coating is obtained, a coating of appropriate thickness will not be obtained, too thin a coating will result in too small a void volume to buffer the volume change, too thick a coating will result in not good mechanical stability of the final silicon carbon structure and a reduction in the volumetric specific energy density of the composite.
Preferably, when the hydrogen-argon mixed gas is used for carbonizing the high polymer material, due to the existence of the reducing atmosphere, silicon oxide can be reduced into a silicon simple substance, the condition that a large amount of energy is needed in a traditional magnesium thermal reduction method is avoided, the internal template agent calcium carbonate can be heated and decomposed, and due to overflow of a product carbon dioxide, a plurality of mesoporous and microporous structures are formed on a surface coating layer for pore forming, so that the hydrogen-argon mixed gas plays a good role in transmission of electrolyte, and the improvement of the performance of the battery is facilitated.
Preferably, the invention is followed by coating with SiO2Layer and after forming the coated carbon layer, the composite material is made to exist Si/SiO2Composite structure, but different from the conventional Si/SiO2A carbon layer is arranged between the inner parts of the composite structure, and the carbon layer can improve the conductivity of the composite material and inhibit the volume expansibility of the composite material in the circulation process on the one hand, so that the composite structure has a good effect.
Preferably, after acid washing, the template agent which is not removed from the hollow interior is further washed out, and the perfect hollow structure can preferentially relieve the volume expansion effect.
In a word, the product can effectively improve the capacity and the cycling stability of the product due to the buffer effect of the hollow structure and the surface carbon on the volume change and the multilayer composite nano structure, so that the product is applied to the field of lithium ion batteries and shows good cycling stability and specific capacity.
Compared with the prior art, the invention has the following advantages:
1. the invention takes calcium carbonate as a template agent to prepare nano hollow Si @ C @ SiO through multilayer coating carbonization2The @ C multilayer structure composite microsphere has good cycle stability and specific capacity.
2. The preparation method is simple and efficient, and is easy to realize large-scale production.
3. The invention uses hydrogen-argon mixed gas for reduction, avoids the traditional magnesium thermal reduction method and uses different carbon sources, and is beneficial to the formation of a carbon coating layer.
Drawings
FIG. 1 is a scanning electron micrograph of calcium carbonate as a templating agent used in the present invention;
fig. 2 is a battery performance test map of the product in the example of the invention.
Detailed Description
The present invention will now be described in detail for the purpose of making the technical content of the present invention more apparent to those skilled in the art, but it should be noted that the description is illustrative only and not construed as limiting the present invention.
Nano hollow Si @ C @ SiO2The preparation method of the @ C multilayer structure composite microsphere comprises the following steps:
step 1: calcium carbonate microspheres are used as a template, a silicon source is used for hydrolyzing the surface of the calcium carbonate microspheres and wrapping the calcium carbonate microspheres to form calcium carbonate @ SiO2；
Step 2: calcium carbonate @ SiO obtained in step 12Putting the microspheres into high-concentration polymer solution, and coating a layer of polymer material on the surfaces of the microspheres to form calcium carbonate @ SiO2@ macromolecular compound;
and step 3: calcium carbonate @ SiO in step 22The @ polymer is transferred into a high-temperature atmosphere furnace and is sintered at high temperature of 800-1200 ℃ in a hydrogen-argon mixed atmosphere;
and 4, step 4: transferring the high-temperature sintering product obtained in the step 3 into an acidic solution, and further washing and removing impurities to obtain a hollow Si @ C composite structure material;
and 5: respectively coating the hollow Si @ C composite structure material obtained in the step 4 with SiO2The layer and the oligomer layer are treated under the hydrothermal condition of 160-200 ℃, and after the reaction is finished, the product is washed by water to obtain the target product nano hollow Si @ C @ SiO2@ C multilayer structure composite microspheres.
Example 1
Adding 50M L deionized water, 10M L ammonia water and 800M L absolute ethyl alcohol into calcium carbonate microspheres serving as a template agent, then mixing 200M L absolute ethyl alcohol and 10M L TEOS, then dropwise adding the mixed solution into the solution at the speed of 5M L/min, filtering out a product after the reaction is finished, mixing the product to be dry, transferring the product into a PVP solution with the concentration of 20% by weight, continuously stirring and dispersing and wrapping, then separating and placing the product into a high-temperature sintering furnace, performing high-temperature carbonization and reduction at 1200 ℃ under a hydrogen-argon mixed atmosphere, taking out the product after the reaction is finished, placing the product into a 1M hydrochloric acid solution for further washing and removing impurities, drying the product, and wrapping SiO again2After the coating is finished, the mixture is transferred into a sucrose solution to be continuously stirred and coated, and after the mixture is stirred for 2 hours, the mixture is transferred into a hydrothermal reactionThe reaction is carried out in a kettle at 180 ℃ for 20 h. After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the product is centrifugally washed and dried to obtain the final product of the nano hollow Si @ C @ SiO2@ C multilayer structure composite microspheres.
Example 2
Adding 50M L deionized water, 10M L ammonia water and 800M L absolute ethyl alcohol into calcium carbonate microspheres serving as a template agent, then mixing 200M L absolute ethyl alcohol and 10M L TEOS, then dropwise adding the mixed solution into the solution at the speed of 5M L/min, filtering out a product after the reaction is finished, mixing the product to be dry, transferring the product into 15% wt PVA solution, continuously stirring and dispersing and wrapping, then separating and placing the product into a high-temperature sintering furnace, performing high-temperature carbonization and reduction at 1100 ℃ under the mixed atmosphere of hydrogen and argon, taking out the product after the reaction is finished, placing the product into 1M hydrochloric acid solution, further washing and removing impurities, drying the product, and wrapping SiO in a wrapping mode again2And after the coating is finished, transferring the mixture into a sucrose solution, continuously stirring and coating the mixture, stirring the mixture for 2 hours, and transferring the mixture into a hydrothermal reaction kettle to react for 20 hours at 180 ℃. After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the product is centrifugally washed and dried to obtain the final product of the nano hollow Si @ C @ SiO2@ C multilayer structure composite microspheres.
Example 3
Adding 60M L deionized water, 10M L ammonia water and 900M L absolute ethyl alcohol into calcium carbonate microspheres serving as a template agent, then mixing 200M L absolute ethyl alcohol and 10M L TEOS, then dropwise adding the mixed solution into the solution at the speed of 5M L/min, filtering out a product after the reaction is finished, mixing the product to be dry, transferring the product into a PS solution with the concentration of 10% by weight, continuously stirring, dispersing and wrapping, then separating and placing the product into a high-temperature sintering furnace, performing high-temperature carbonization and reduction at 1200 ℃ under a hydrogen-argon mixed atmosphere, taking out the product after the reaction is finished, placing the product into a 1M hydrochloric acid solution for further washing and removing impurities, drying the product, and wrapping SiO again2After the coating is finished, the mixture is transferred into a sucrose solution to be continuously stirred and coated, and after the mixture is stirred for 2 hours, the mixture is transferred into a hydrothermal reaction kettle to react for 18 hours at 190 DEG C. After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the product is centrifugally washed and dried to obtain the final product of the nano hollow Si @ C @ SiO2@ C multilayer structure composite microspheres.
Example 4
Adding 50M L deionized water, 15M L ammonia water and 850M L absolute ethyl alcohol into calcium carbonate microspheres serving as a template agent, mixing 300M L absolute ethyl alcohol and 10M L TEOS, dropwise adding the mixed solution into the solution at the speed of 3M L/min, filtering out a product after the reaction is finished, drying the product, transferring the dried product into a PVP solution with the concentration of 20% by weight, continuously stirring, dispersing and wrapping the product, separating the product, placing the product into a high-temperature sintering furnace, performing high-temperature carbonization and reduction at 1200 ℃ under a hydrogen-argon mixed atmosphere, taking out the product after the reaction is finished, placing the product into 1M nitric acid solution for further washing to remove impurities, drying the product, and wrapping SiO in the product again2And after the coating is finished, transferring the mixture into a sucrose solution, continuously stirring and coating the mixture, stirring the mixture for 2 hours, and transferring the mixture into a hydrothermal reaction kettle to react for 20 hours at 180 ℃. After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the product is centrifugally washed and dried to obtain the final product of the nano hollow Si @ C @ SiO2@ C multilayer structure composite microspheres.
Example 5
Adding 60M L deionized water, 10M L ammonia water and 800M L absolute ethyl alcohol into calcium carbonate microspheres serving as a template agent, then mixing 200M L absolute ethyl alcohol and 10M L TEOS, then dropwise adding the mixed solution into the solution at the speed of 3M L/min, filtering out a product after the reaction is finished, mixing the product to be dry, transferring the product into a PVP solution with the concentration of 20% by weight, continuously stirring and dispersing and wrapping, then separating and placing the product into a high-temperature sintering furnace, performing high-temperature carbonization and reduction at 1200 ℃ under a hydrogen-argon mixed atmosphere, taking out the product after the reaction is finished, placing the product into a 0.5M sulfuric acid solution for further washing and removing impurities, drying the product, and wrapping SiO again2And after the coating is finished, transferring the mixture into a sucrose solution, continuously stirring and coating the mixture, stirring the mixture for 2 hours, and transferring the mixture into a hydrothermal reaction kettle to react for 20 hours at 180 ℃. After the reaction is finished, the reaction is carried outNaturally cooling the reaction kettle to room temperature, centrifugally washing and drying the product to obtain the final product of the nano hollow Si @ C @ SiO2@ C multilayer structure composite microspheres.

Claims (9)

1. Nano hollow Si @ C @ SiO2The preparation method of the @ C multilayer structure composite microsphere is characterized by comprising the following steps of:
step 1: calcium carbonate microspheres are used as a template, a silicon source is used for hydrolyzing the surface of the calcium carbonate microspheres and wrapping the calcium carbonate microspheres to form calcium carbonate @ SiO2；
Step 2: calcium carbonate @ SiO obtained in step 12Putting the microspheres into high-concentration polymer solution, and coating a layer of polymer material on the surfaces of the microspheres to form calcium carbonate @ SiO2@ macromolecular compound;
and step 3: calcium carbonate @ SiO in step 22The @ polymer is transferred into a high-temperature atmosphere furnace and is sintered at high temperature of 800-1200 ℃ in a hydrogen-argon mixed atmosphere;
and 4, step 4: transferring the high-temperature sintering product obtained in the step 3 into an acidic solution, and further washing and removing impurities to obtain a hollow Si @ C composite structure material;
and 5: respectively coating the hollow Si @ C composite structure material obtained in the step 4 with SiO2The layer and the oligomer layer are treated under the hydrothermal condition of 160-200 ℃, and after the reaction is finished, the product is washed by water to obtain the target product nano hollow Si @ C @ SiO2@ C multilayer structure composite microspheres.
2. The nano hollow Si @ C @ SiO of claim 12The preparation method of the @ C multilayer structure composite microsphere is characterized in that the silicon source is selected from one of TEOS or sodium silicate.
3. The nano hollow Si @ C @ SiO of claim 12The preparation method of the @ C multilayer structure composite microsphere is characterized in that the polymer is one of PVA, PVP and PS.
4. A nanohole as in claim 1Core Si @ C @ SiO2The preparation method of the @ C multilayer structure composite microsphere is characterized in that the acidic solution is one of hydrochloric acid, nitric acid or sulfuric acid.
5. The nano hollow Si @ C @ SiO of claim 12The preparation method of the @ C multilayer structure composite microsphere is characterized in that the oligomer refers to one of glucose, sucrose or fructose.
6. The nano hollow Si @ C @ SiO of claim 12The preparation method of the @ C multilayer structure composite microsphere is characterized in that the hydrothermal treatment time is 16-28 h.
7. The nano hollow Si @ C @ SiO of claim 12The preparation method of the @ C multilayer structure composite microsphere is characterized in that the volume ratio of deionized water to ammonia water to absolute ethyl alcohol is 5-8: 1-2: 80-90; the volume ratio of the absolute ethyl alcohol to the TEOS is 20-30: 1.
8. The nano hollow Si @ C @ SiO prepared by the method of any one of claims 1 to 72@ C multilayer structure composite microspheres.
9. The nano-scale hollow Si @ C @ SiO of claim 82The application of the @ C multilayer structure composite microspheres in the lithium ion battery cathode material.
CN202010328877.9A 2020-04-23 2020-04-23 Nano hollow Si @ C @ SiO2@ C multilayer structure composite microsphere and preparation method and application thereof Pending CN111416114A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112038618A (en) * 2020-09-04 2020-12-04 中国有色桂林矿产地质研究院有限公司 Nano silicon powder polymeric sphere composite negative electrode material with hollow structure and preparation method and application thereof
CN112044372A (en) * 2020-09-19 2020-12-08 复旦大学 Hollow titanium dioxide @ carbon composite microsphere and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112038618A (en) * 2020-09-04 2020-12-04 中国有色桂林矿产地质研究院有限公司 Nano silicon powder polymeric sphere composite negative electrode material with hollow structure and preparation method and application thereof
CN112044372A (en) * 2020-09-19 2020-12-08 复旦大学 Hollow titanium dioxide @ carbon composite microsphere and preparation method thereof
CN112044372B (en) * 2020-09-19 2022-06-21 复旦大学 Hollow titanium dioxide @ carbon composite microsphere and preparation method thereof

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