CN113823785A - Hollow mesoporous carbon shell coated metal nanosphere and super-assembly preparation method and application thereof - Google Patents

Hollow mesoporous carbon shell coated metal nanosphere and super-assembly preparation method and application thereof Download PDF

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CN113823785A
CN113823785A CN202111111273.XA CN202111111273A CN113823785A CN 113823785 A CN113823785 A CN 113823785A CN 202111111273 A CN202111111273 A CN 202111111273A CN 113823785 A CN113823785 A CN 113823785A
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mesoporous carbon
metal
hollow mesoporous
carbon shell
nanosphere
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CN113823785B (en
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李勇
乔利
李东玮
许冠辰
王猛
高萌
梁秀
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New Material Institute of Shandong Academy of Sciences
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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Abstract

The invention discloses a hollow mesoporous carbon shell coated metal nanosphere, and a super-assembly preparation method and application thereof, and belongs to the technical field of lithium ion battery material preparation. The super-assembly preparation method of the hollow mesoporous carbon shell coated metal nanosphere comprises the following steps: and sequentially adding tetraethoxysilane, ammonia water, resorcinol and formaldehyde into the metal nanosphere solution, uniformly mixing, and then carrying out pyrolysis and etching to obtain the hollow mesoporous carbon shell coated metal nanospheres. The preparation method is simple and has wide applicability, and the prepared hollow mesoporous carbon shell coated metal nanospheres are used as a carrier of a lithium anode material, so that the problems that the shuttle effect of the material taking lithium as an anode is poor and lithium dendrites are easily generated are effectively solved. The metal salt hydrate adopted by the invention has lower cost, and the solvent adopts water and ethanol, so the invention has the characteristics of no pollution and low price, and the application range relates to the fields of electro-catalytic materials, lithium-sulfur batteries, lithium metal batteries and the like.

Description

Hollow mesoporous carbon shell coated metal nanosphere and super-assembly preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion battery material preparation, in particular to a hollow mesoporous carbon shell coated metal nanosphere and a super-assembly preparation method and application thereof.
Background
The growing demand for clean, sustainable power systems for consumer electronics, electric vehicles and national grid storage has driven the development of electrochemical energy storage systems with better safety, lower cost and higher energy density than current lithium ion batteries. Among other competitors, lithium-sulfur (Li-S) batteries are considered an outstanding representative because of their high theoretical capacity (S: 1675mAh/g and Li: 3860mAh/g), S sustainability, and Li' S lowest reduction potential (-3.04V vs. standard hydrogen electrodes). Despite decades of effort, lithium sulfur batteries still suffer from some of the deleterious problems associated with the cathode and anode. For sulfur cathodes, the diffusion of the intermediate lithium polysulfide and slow sulfur redox conversion kinetics lead to poor specific capacity, poor rate performance and rapid capacity degradation. For lithium anodes, uncontrolled dendrite growth and infinite volume expansion lead to safety risks and low coulombic efficiency. Therefore, it is imperative to design kinetically advanced lithium sulfur battery systems with good structures for lithium polysulfide suppression type cathodes and dendrite-free type anodes.
The hollow carbon sphere nanoreactor, which has good electrical conductivity, a large surface area and enhanced structural stability, is gradually becoming a research hotspot in recent years, and has been widely used as a main body of a secondary battery to improve electrochemical performance thereof. For example, as a sulfur cathode, a hollow porphyrin organic framework is designed for long cycle stability of lithium sulfur batteries. In addition, researchers have also explored double-layered hollow carbon spheres as independent sulfur carriers for high energy density lithium sulfur batteries. For application in lithium metal batteries as lithium metal anodes, encapsulation of lithium into hollow carbon spheres is designed for high stability lithium metal anodes. However, lithium dendrites are not substantially solved only by designing the material of the lithium anode using the hollow carbon sphere nanoreactor, because the physical effect solves only the surface problem, not the fundamental problem.
Disclosure of Invention
The invention aims to provide a hollow mesoporous carbon shell coated metal nanosphere and a super-assembly preparation method and application thereof, aiming at solving the problems in the prior art, the hollow mesoporous carbon shell coated metal nanosphere is obtained by sequentially adding tetraethoxysilane, ammonia water, resorcinol and formaldehyde into a metal nanosphere solution, uniformly mixing, and then pyrolyzing and etching, and the hollow mesoporous carbon shell coated metal nanosphere is used as a carrier of a lithium anode material, so that the problem that lithium dendrite is easily generated on the material taking lithium as an anode is effectively solved.
In order to achieve the purpose, the invention provides the following scheme:
one of the technical schemes of the invention is as follows: a hollow mesoporous carbon shell is coated with metal nanospheres, and the hollow mesoporous carbon shell is coated with the metal nanospheres; the size of the hollow mesoporous carbon shell is 200-300 nm; the size of the metal nanosphere is 50-100 nm.
The second technical scheme of the invention is as follows: a super-assembly preparation method of the hollow mesoporous carbon shell coated metal nanosphere comprises the following steps: and sequentially adding tetraethoxysilane, ammonia water, resorcinol and formaldehyde into the metal nanosphere solution, uniformly mixing, and then carrying out pyrolysis and etching to obtain the hollow mesoporous carbon shell coated metal nanospheres.
Further, the metal nanosphere solution is a mixed solution of metal nanospheres dissolved in an ethanol aqueous solution.
Further, the preparation of the metal nanosphere specifically comprises: mixing a metal salt solution and polyvinylpyrrolidone, and then carrying out hydrothermal reaction and calcination to obtain the metal nanospheres; the metal salt solution is a saturated solution of metal salt in methanol; the mass ratio of the metal salt to the polyvinylpyrrolidone is 1: 1-1: 3.
Further, the metal salt is selected from stannous chloride, zinc chloride, bismuth chloride or bismuth nitrate.
Further, the temperature of the hydrothermal reaction is 160-200 ℃, and the time is 1-4 hours; the calcining temperature is 550-650 ℃, and the time is 1-3 h.
Further, the ratio of the metal nanospheres to ethyl orthosilicate is 1.0-2.0 g: 2-4 mL.
Further, the pyrolysis specifically comprises: heating to 650-750 ℃ at a heating rate of 1-5 ℃/min, and preserving heat for 3-6 h.
Further, the chemical reagent used for etching includes any one of hydrofluoric acid or sodium hydroxide.
The third technical scheme of the invention is as follows: an application of the metal nanosphere coated with the hollow mesoporous carbon shell in preparing electrocatalytic materials, lithium-sulfur batteries and lithium metal batteries.
The invention discloses the following technical effects:
according to the invention, tetraethoxysilane, ammonia water, resorcinol and formaldehyde are sequentially added into a metal nanosphere solution, uniformly mixed and then pyrolyzed and etched to obtain a hollow mesoporous carbon shell coated metal nanosphere with excellent performance, the size of the obtained hollow mesoporous carbon shell is 200-300 nm, the shape of the obtained hollow mesoporous carbon shell is spherical, the coated metal nanosphere is oval or round, the size of the coated metal nanosphere is 50-100 nm, and the nano reactor can be used in the fields of electro-catalytic materials, lithium-sulfur batteries, lithium metal batteries and the like, and has the advantages of high specific surface area, multi-stage pore structures, good lithium-philic metal surfaces and excellent catalytic activity. The catalyst is simultaneously applied to the anode and the cathode of the lithium-sulfur battery, so that the adsorption catalytic conversion capacity of the anode to polysulfide is effectively improved, and the growth of lithium dendrite of the cathode can be remarkably inhibited. The hollow mesoporous carbon shell coated metal nanospheres are used as a carrier of a lithium anode material, so that the problems that the shuttle effect of lithium as the anode material is poor and lithium dendrites are easy to generate are effectively solved.
The raw materials used in the invention are common metal salt hydrates, the cost is low, the preparation method is simple, the applicability is wide, and the preparation method is suitable for large-scale production; the solvent adopts water and ethanol, and has the characteristics of no pollution and low price. The super-assembly preparation method of the hollow mesoporous carbon-coated metal nanosphere is suitable for large-scale industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a Scanning Electron Microscope (SEM) image of tin dioxide nanospheres prepared in example 1 of the present invention;
fig. 2 is a Scanning Electron Microscope (SEM) image of the tin nanosphere coated with the hollow mesoporous carbon shell prepared in example 1 of the present invention;
fig. 3 is a Transmission Electron Microscope (TEM) image of the tin nanosphere coated with the hollow mesoporous carbon shell prepared in example 1 of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
A super-assembly preparation method of a hollow mesoporous carbon shell coated metal nanosphere comprises the following steps:
(1) 0.35g of stannous chloride pentahydrate and 0.5g of polyvinylpyrrolidone are mixed and dissolved in 60mL of methanol to obtain a mixed solution, then the mixed solution is put into a high-pressure hydrothermal kettle for hydrothermal reaction at 180 ℃ for 3h, the product after hydrothermal reaction is cleaned by methanol and then put into an oven for drying, and then the product is put into a muffle furnace for calcining at 600 ℃ for 2h to obtain the tin dioxide nanospheres (shown in a SEM picture in figure 1).
(2) Ultrasonically dispersing the tin dioxide nanospheres prepared in the step (1) in an ethanol water solution with the volume fraction of 87.5%, sequentially adding 3.46mL of ethyl orthosilicate and 3mL of ammonia water, stirring at the room temperature of 800r/min for 15min, then stirring at the room temperature, adding 0.4g of resorcinol and 0.56mL of formaldehyde, stirring at the room temperature of 600r/min for 24h, centrifuging, washing with water and absolute ethyl alcohol, and drying to obtain the silicon dioxide coated tin dioxide nanospheres.
(3) And (3) putting the silicon dioxide coated tin dioxide nanospheres obtained in the step (2) into a tube furnace, heating to 700 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, preserving the temperature for 5h, then etching by using 20 wt% hydrofluoric acid, and removing silicon dioxide in the tin dioxide nanospheres to obtain the tin nanospheres coated by the hollow mesoporous carbon shell, wherein an SEM picture is shown in figure 2, and a TEM picture is shown in figure 3.
Example 2
The difference from example 1 is that stannous chloride pentahydrate in step (1) is replaced with zinc chloride.
Example 3
The difference from example 1 is that stannous chloride pentahydrate in step (1) is replaced with bismuth chloride.
Example 4
The difference from example 1 is that stannous chloride pentahydrate in step (1) is replaced with bismuth nitrate.
Example 5
(1) 0.35g of stannous chloride pentahydrate and 0.35g of polyvinylpyrrolidone are mixed and dissolved in 60mL of methanol to obtain a mixed solution, the mixed solution is put into a high-pressure hydrothermal kettle for hydrothermal reaction for 1h at 160 ℃, the product after hydrothermal reaction is cleaned by methanol and then put into an oven for drying, and then the product is put into a muffle furnace for calcining for 1h at 550 ℃ to obtain the tin dioxide nanospheres.
(2) Ultrasonically dispersing the tin dioxide nanospheres prepared in the step (1) in an ethanol water solution with the volume fraction of 87.5%, sequentially adding 3.46mL of ethyl orthosilicate and 3mL of ammonia water, stirring vigorously at room temperature for 15min, then adding 0.4g of resorcinol and 0.56mL of formaldehyde, stirring at room temperature for 24h, centrifuging, washing with water and ethanol, and drying to obtain the silicon dioxide coated tin dioxide nanospheres.
(3) And (3) putting the silicon dioxide coated tin dioxide nanospheres obtained in the step (2) into a tube furnace, heating to 650 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, preserving the heat for 3 hours, then etching by using 20% sodium hydroxide, and removing the silicon dioxide in the tin dioxide nanospheres to obtain the tin nanospheres coated by the hollow mesoporous carbon shell.
Example 6
(1) 0.35g of stannous chloride pentahydrate and 1.05g of polyvinylpyrrolidone are mixed and dissolved in 60mL of methanol to obtain a mixed solution, the mixed solution is put into a high-pressure hydrothermal kettle for hydrothermal reaction for 4 hours at 200 ℃, the product after hydrothermal reaction is cleaned by methanol and then put into an oven for drying, and then the product is put into a muffle furnace for calcining for 3 hours at 650 ℃ to obtain the tin dioxide nanospheres.
(2) Ultrasonically dispersing the tin dioxide nanospheres prepared in the step (1) in an ethanol water solution with the volume fraction of 87.5%, sequentially adding 3.46mL of ethyl orthosilicate and 3mL of ammonia water, stirring vigorously at room temperature for 15min, then adding 0.4g of resorcinol and 0.56mL of formaldehyde, stirring at room temperature for 24h, centrifuging, washing with water and ethanol, and drying to obtain the silicon dioxide coated tin dioxide nanospheres.
(3) And (3) putting the silicon dioxide coated tin dioxide nanospheres obtained in the step (2) into a tube furnace, heating to 750 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, preserving the heat for 6 hours, then etching by using 20% sodium hydroxide, and removing the silicon dioxide in the tin dioxide nanospheres to obtain the tin nanospheres coated by the hollow mesoporous carbon shell.
Comparative example 1
(1) 0.35g of stannous chloride pentahydrate and 0.5g of polyvinylpyrrolidone are mixed and dissolved in 60mL of methanol to obtain a mixed solution, then the mixed solution is put into a high-pressure hydrothermal kettle for hydrothermal reaction at 180 ℃ for 3h, the product after hydrothermal reaction is cleaned by methanol and then put into an oven for drying, and then the product is put into a muffle furnace for calcining at 600 ℃ for 2h to obtain the tin dioxide nanospheres.
(2) Ultrasonically dispersing the tin dioxide nanospheres prepared in the step (1) in an ethanol water solution with the volume fraction of 87.5%, sequentially adding 3.46mL of ethyl orthosilicate and 3mL of ammonia water, stirring vigorously at room temperature (800r/min) for 15min, then stirring at room temperature, adding 0.4g of resorcinol and 0.56mL of formaldehyde, stirring at room temperature (600r/min) for 5h, and centrifuging to obtain the tin nanospheres wrapped by the silicon dioxide, wherein the stirring time is too short, and the silicon dioxide nanospheres cannot be formed.
Effect example 1
The lithium metal full cell assembled by the composite negative electrode realizes that the capacity attenuation rate is only 3% under the condition of 600 cycles of long cycle, and can still keep high rate performance under the condition of high current density 8C, and the lithium metal full cell can effectively enable lithium ions to be uniformly deposited and inhibit the formation of lithium dendrites when used as the lithium metal negative electrode.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (10)

1. A metal nanosphere is coated on a hollow mesoporous carbon shell, and is characterized in that the metal nanosphere is coated in the hollow mesoporous carbon shell; the size of the hollow mesoporous carbon shell is 200-300 nm; the size of the metal nanosphere is 50-100 nm.
2. The super-assembly preparation method of the hollow mesoporous carbon shell coated metal nanosphere according to claim 1, characterized by comprising the following steps: and sequentially adding tetraethoxysilane, ammonia water, resorcinol and formaldehyde into the metal nanosphere solution, uniformly mixing, and then carrying out pyrolysis and etching to obtain the hollow mesoporous carbon shell coated metal nanospheres.
3. The method for preparing a super assembly of the hollow mesoporous carbon shell coated metal nanosphere according to claim 1, wherein the metal nanosphere solution is a mixed solution of metal nanospheres dissolved in an ethanol aqueous solution.
4. The method for preparing the metal nanospheres with the hollow mesoporous carbon shells in a super-assembly manner according to claim 3, wherein the preparation of the metal nanospheres specifically comprises the following steps: mixing a metal salt solution and polyvinylpyrrolidone, and then carrying out hydrothermal reaction and calcination to obtain the metal nanospheres; the metal salt solution is a saturated solution of metal salt in methanol; the mass ratio of the metal salt to the polyvinylpyrrolidone is 1: 1-1: 3.
5. The method for preparing the hollow mesoporous carbon shell coated metal nanosphere according to claim 4, wherein the metal salt is selected from stannous chloride, zinc chloride, bismuth chloride or bismuth nitrate.
6. The method for preparing the super-assembly of the hollow mesoporous carbon shell coated metal nanosphere according to claim 4, wherein the temperature of the hydrothermal reaction is 160-200 ℃ and the time is 1-4 h; the calcining temperature is 550-650 ℃, and the time is 1-3 h.
7. The super-assembly preparation method of the hollow mesoporous carbon shell coated metal nanosphere according to claim 1, wherein the ratio of the metal nanosphere to tetraethoxysilane is 1.0-2.0 g: 2-4 mL.
8. The method for preparing the hollow mesoporous carbon shell coated metal nanosphere in a super-assembly manner according to claim 1, wherein the pyrolysis specifically comprises: heating to 650-750 ℃ at a heating rate of 1-5 ℃/min, and preserving heat for 3-6 h.
9. The method for preparing the hollow mesoporous carbon shell coated metal nanosphere in a super-assembly manner according to claim 1, wherein the chemical reagent used for etching comprises any one of hydrofluoric acid and sodium hydroxide.
10. Use of the hollow mesoporous carbon shell coated metal nanosphere of claim 1 in the preparation of electrocatalytic materials, lithium sulfur batteries and lithium metal batteries.
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CN101623634A (en) * 2009-08-04 2010-01-13 厦门大学 Nuclear shell nanometer catalyst packaged with noble metal nanometer grains and method thereof
JP2011168437A (en) * 2010-02-18 2011-09-01 Nagoya Institute Of Technology Method for producing hollow particles
CN102208616A (en) * 2011-05-09 2011-10-05 北京化工大学 Preparation method of carbon-coated transition metal nano hollow particle
CN107442111A (en) * 2016-05-30 2017-12-08 中国科学院长春应用化学研究所 Carbon-clad metal nanocube material and preparation method thereof
CN108199032A (en) * 2018-01-20 2018-06-22 西南大学 The preparation of the hollow bismuth simple substance of carbon-coated nano and its alkaline battery application
CN111232985A (en) * 2020-01-17 2020-06-05 昆明理工大学 Preparation method of micron-sized porous hollow silicon spheres
CN111755668A (en) * 2019-03-26 2020-10-09 中南大学 Nitrogen-oxygen co-doped carbon-coated metal lithium anode active material, anode, lithium metal battery and preparation and application thereof
CN113363434A (en) * 2021-05-12 2021-09-07 中国科学院过程工程研究所 Multi-core multi-shell hollow material for encapsulating nano particles and preparation method and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101623634A (en) * 2009-08-04 2010-01-13 厦门大学 Nuclear shell nanometer catalyst packaged with noble metal nanometer grains and method thereof
JP2011168437A (en) * 2010-02-18 2011-09-01 Nagoya Institute Of Technology Method for producing hollow particles
CN102208616A (en) * 2011-05-09 2011-10-05 北京化工大学 Preparation method of carbon-coated transition metal nano hollow particle
CN107442111A (en) * 2016-05-30 2017-12-08 中国科学院长春应用化学研究所 Carbon-clad metal nanocube material and preparation method thereof
CN108199032A (en) * 2018-01-20 2018-06-22 西南大学 The preparation of the hollow bismuth simple substance of carbon-coated nano and its alkaline battery application
CN111755668A (en) * 2019-03-26 2020-10-09 中南大学 Nitrogen-oxygen co-doped carbon-coated metal lithium anode active material, anode, lithium metal battery and preparation and application thereof
CN111232985A (en) * 2020-01-17 2020-06-05 昆明理工大学 Preparation method of micron-sized porous hollow silicon spheres
CN113363434A (en) * 2021-05-12 2021-09-07 中国科学院过程工程研究所 Multi-core multi-shell hollow material for encapsulating nano particles and preparation method and application thereof

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