CN113540456A - Metal oxide composite material and preparation method and application thereof - Google Patents

Metal oxide composite material and preparation method and application thereof Download PDF

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Publication number
CN113540456A
CN113540456A CN202110627162.8A CN202110627162A CN113540456A CN 113540456 A CN113540456 A CN 113540456A CN 202110627162 A CN202110627162 A CN 202110627162A CN 113540456 A CN113540456 A CN 113540456A
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acetylene black
metal oxide
composite material
oxide composite
acid
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朱立才
史晴
程节
周月
袁中直
潘燕霞
吴钰佳
罗薪涛
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South China Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide (Fe2O3)
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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

The invention discloses a metal oxide composite material and a preparation method and application thereof. The invention utilizes the industrialized conductive carbon acetylene black with excellent conductivity as a carbon source to form the hollow carbon sphere packaging metal oxide which can be used as a cathode material of a high-performance lithium ion battery and shows high reversible capacity and excellent cycle performance and rate capability.

Description

Metal oxide composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a metal oxide composite material and a preparation method and application thereof.
Background
With the rapid development of portable electronic products, the demands for novel electrode materials with high specific capacity and simple low-cost preparation methods are becoming more urgent. In recent years, Lithium Ion Batteries (LIBs) have been the mainstay of driving the explosion of portable electronic technology. In the field of rechargeable lithium ion batteries, carbon materials such as graphite and hard carbon are commonly used as negative electrode materials. However, the theoretical specific capacity of carbon is low, limiting its development. Compared with the current commercial electrode material, Fe2O3Due to the characteristics of large theoretical charge capacity, wide availability, no toxicity and the like, the method has attracted extensive attention of people. Fe2O3The theoretical capacity of the graphite is up to 1007mA h/g, which is far higher than that of the graphite (372mAh/g) used at present. In principle, Fe2O3The lithium storage capacity of (A) is mainly determined by Li+With Fe2O3By reversible transformation reactions between Li and Li during the reaction2Fe Nanoparticles (NPs) in an O matrix. However, such conversion reactions often cause drastic volume changes and severe structural damage, resulting in Fe2O3The capacity fading is fast and the cyclicity is poor. Further, Fe2O3The low conductivity and slow electrode kinetics of (a) are also very detrimental to its lithium storage.
Nano Fe2O3Bonding ofThe carbon coating strategy has been extensively studied to improve Fe content2O3The capacity retention stability and conductivity of LIBs electrodes of (a). Nano Fe2O3The nano composite material obtained by combining carbon coating has huge specific surface area, can shorten the transport path of electrons/ions and obviously reduce volume expansion, and the carbon component in the nano composite material can provide enough buffer for the rapid expansion of the electrons/ions and obviously contributes to the electron conductivity. The carbon coating layer prevents direct contact of the active phase with the electrolyte, thereby preventing continuous decomposition of the electrolyte, and thus improving the cycle stability of the electrode. Chai et al synthesized Fe in two steps using glucose as carbon source2O3@ C nanospheres having a discharge capacity of 826.2mAh/g after 20 cycles at 0.1A/g. Zhang et al uses resorcinol formaldehyde resin solution to prepare three-dimensional porous Fe by aerosol spray pyrolysis technology2O3@ C nanocomposite. The reversible capacity of the electrode was 358mAh/g through 1400 cycles even at a high current density of 2A/g.
Although carbon coated Fe2O3The study of @ C has made great progress, but in most cases Fe2O3The production method of @ C often requires a complicated experimental process, and Fe needs to be prepared firstly2O3The nanoparticles, then the carbon shell coated, inevitably show Fe2O3Severe aggregation and non-uniformity of the carbon coating. The carbon precursor is widely applied to carbon coating, and due to the fact that a carbon source such as glucose, oleic acid, glycol or ionic liquid is used in the carbon coating process, the product complexity is caused, and volatile organic compounds CO and CO can be generated through thermal decomposition of the product2Environmental problems are caused, and the graphitization degree of the carbon layer is generally not high, which has adverse effects on the structure and performance of the composite material.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a metal oxide composite material which has the characteristics of high specific capacity and excellent cycle performance and rate capability.
Meanwhile, the invention also provides a preparation method and application of the metal oxide composite material.
Specifically, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a metal oxide composite material, which contains acetylene black hollow nanospheres, wherein metal oxide is encapsulated inside the acetylene black hollow nanospheres.
The metal oxide composite material according to the first aspect of the present invention has at least the following advantageous effects:
the invention uses acetylene black as carbon source to package metal oxide, the acetylene black is acetylene with purity of more than 99% which is obtained by decomposing and refining by-product gas generated in the process of calcium carbide method or crude gasoline pyrolysis, carbon black obtained by continuous pyrolysis and gaseous carbon source (such as CH)4) Compared with other organic carbon sources, a more highly graphitized shell layer is formed on the surface of the metal oxide nano particle, and the conductivity is higher. In addition, in a core-shell structure formed by the acetylene black hollow nanospheres and the metal oxide, the metal oxide is wrapped by the acetylene black with high crystallinity and stability, and the unique chain-branch structures of the acetylene black are connected with each other, so that a conductive network for effective electron transfer is provided, and a space is provided in a circulating process to buffer the volume expansion of the metal oxide so as to enhance the structural stability of the electrode. Based on these characteristics, the metal oxide composite material of the present invention exhibits high reversible capacity and excellent cycle performance, and has great potential as a high-performance negative electrode material for LIBs.
In some embodiments of the invention, the metal oxide comprises Fe2O3、Fe3O4、Co3O4、CoO、NiO、TiO2Preferably Fe2O3。
In some embodiments of the invention, the particle size of the acetylene black hollow nanospheres is 30-60 nm, and the pore diameter inside the acetylene black hollow nanospheres is 10-30 nm, preferably 15-20 nm.
In some embodiments of the invention, the acetylene black hollow core is sodiumThe specific surface area of the rice ball is 150-250 m2A concentration of 180 to 200m2(ii)/g; the pore volume of the acetylene black hollow nanospheres is 0.1-1 cm3A/g, preferably 0.3 to 0.8cm3/g。
In some embodiments of the present invention, the metal oxide is converted from a metal salt encapsulated inside an acetylene black hollow nanosphere, and the mass ratio of the acetylene black hollow nanosphere to the metal salt is 1: 4-10, preferably 1: 5 to 8.
The second aspect of the present invention provides a method for preparing the above metal oxide composite material, comprising the steps of:
etching the acetylene black to obtain acetylene black hollow nanospheres; and encapsulating metal salt into the acetylene black hollow nanospheres, and calcining to obtain the metal oxide composite material.
In some embodiments of the invention, the method of etching is acid etching. More specifically, acetylene black is mixed with oxidizing acid and reacted to obtain the acetylene black hollow nanosphere.
In some embodiments of the present invention, the oxidizing acid includes one or more of concentrated nitric acid (with a mass concentration of 50% to 70%), concentrated sulfuric acid (with a mass concentration of 70% or more), permanganic acid, and perchloric acid, preferably concentrated nitric acid.
In some embodiments of the invention, the temperature of the reaction is 120 to 200 ℃, preferably 130 to 160 ℃.
In some embodiments of the invention, the reaction is carried out in a closed environment.
The oxidizing acid can chemically oxidize the acetylene black to form a hollow structure. According to the formation mechanism and microstructure of acetylene black, sp3 of acetylene black particles tends to be preferentially oxidized in more hybridized interiors and react with acid more easily. In a sealed oxidation device, high temperature can cause the evaporation and reflux of oxidizing acid, and the formed high pressure is favorable for the acid to diffuse through the pores and the pores of the acetylene black, and once the acid reaches the less developed carbon structure and more sp3 hybridized internal centers in the acetylene black nanospheres, the oxidation begins to occur. In this case, more defect sites are generated in the intensive oxidation process and result in an increase in reactivity, forming hollow nanostructures.
In some embodiments of the present invention, the metal salt is encapsulated inside the acetylene black hollow nanospheres by mixing a metal salt solution with the acetylene black hollow nanospheres and maintaining the mixture under vacuum for a certain period of time. The metal salt can be successfully encapsulated inside the acetylene black hollow nanospheres by a vacuum filling method.
In some embodiments of the invention, the metal salt solution is an alcoholic solution of a metal salt. The metal salt comprises one or more of nitrate and hydrate of metal, chloride and hydrate of metal, sulfate and hydrate of metal, bromide and hydrate of metal, fluoride and hydrate of metal. For example, when the metal oxide is Fe2O3When the metal salt is ferric salt, the ferric salt comprises one or more of ferric nitrate and hydrate thereof, ferric chloride and hydrate thereof, ferric sulfate and hydrate thereof, ferric bromide and hydrate thereof, and ferric fluoride and hydrate thereof. The alcohol solution takes alcohol as a solvent, and the alcohol is small molecular alcohol and comprises any one or more of ethanol, methanol, butanol and propylene glycol. The surface tension of alcohol is smaller than that of water, for example, the surface tension of ethanol is 22.39mN/m at 25 ℃, and is much smaller than that of water (72.0mN/m), the additional pressure required under the same conditions with an alcohol solution is much smaller than that of an aqueous solution, and the iron-containing solution is easier to be introduced into the hollow nanocarbon nanospheres with alcohol.
In some embodiments of the invention, the metal salt solution has a concentration of 5 to 20 g/mL.
In some embodiments of the invention, the mass ratio of acetylene black to metal salt is 1: 4-10, preferably 1: 5 to 8.
In some embodiments of the invention, the pressure under vacuum is 0 to 0.1 Pa; the time for keeping under the vacuum condition is 0.5-10 h, preferably 0.5-5 h. In actual operation, the vacuum pumping can be performed for several times.
In some embodiments of the invention, the temperature of the calcination is 150 to 300 ℃, preferably 190 to 230 ℃; the calcining time is 0.5-5 h, preferably 1-3 h.
A third aspect of the invention provides the use of the metal oxide for the manufacture of an electrode or a lithium battery. In a lithium battery, the electrode containing the iron oxide may serve as a negative electrode.
Compared with the prior art, the invention has the following beneficial effects:
the invention utilizes the industrialized conductive carbon acetylene black with excellent conductivity as a carbon source to form the hollow carbon sphere packaging metal oxide which can be used as a cathode material of a high-performance lithium ion battery and shows high reversible capacity and excellent cycle performance and rate capability.
The preparation method directly utilizes the hollow carbon spheres made of acetylene black with high graphitization degree as the carbon shell, and then utilizes vacuum filling to fill the active substances into the carbon shell.
Drawings
FIG. 1 is a transmission electron microscope image of hollow carbon nanospheres at different magnifications;
FIG. 2 shows Acetylene Black (ABs), hollow carbon nanoballs (HABs) and Fe2O3The pore size distribution plot of @ C;
FIG. 3 shows Acetylene Black (ABs), hollow carbon nanoballs (HABs) and Fe2O3A nitrogen adsorption-desorption curve of @ C;
FIG. 4 is Fe2O3The transmission electron microscope image and the element distribution diagram of @ C;
FIG. 5 is Fe2O3@ C electrostatic current charge-discharge curve at 0.1A/g current;
FIG. 6 is Fe2O3@ C discharge curves (a) and Fe at different current densities2O3@C、Fe2O3Cyclic discharge curve at 0.1A/g current;
FIG. 7 is Fe2O3@ C and Fe2O3The result of the rate capability test.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
Examples
Preparing a composite material:
(1) preparation of hollow nanospheres
2g of Acetylene Black (ABs) is put into a polytetrafluoroethylene reaction liner, and about 35ml of concentrated nitric acid (65-68 percent, analytically pure) is added and mixed evenly; putting the mixture into a high-pressure reaction kettle, and heating the mixture in a blast oven at 150 ℃ for 20 hours; after cooling to room temperature, washing to neutrality by using absolute ethyl alcohol and distilled water respectively; dried in a forced air oven at 70 ℃ for 12 hours to obtain hollow carbon nanoballs (HABs).
The transmission electron microscope image of the hollow carbon nanosphere is shown in fig. 1. It can be seen from fig. 1 that the hollow carbon nanoball has the hollow nano-particles having the uniform particle size distribution, and the particle size distribution of the hollow carbon nanoball is about 50 nm.
Tests show that before acid treatment, the pore diameter of the Acetylene Black (ABs) is mainly distributed around 2nm, and the specific surface area is 66.35m2Per g, pore volume of 0.19cm3(ii)/g; and the specific surface area of the hollow carbon nanoballs (HABs) formed after the acid treatment is 195.51m2Per g, pore volume of 0.39cm3(ii)/g, contains mesopores distributed in 15-20 nm, as shown in FIGS. 2 and 3. The test result shows that the specific surface area and the total pore volume of the hollow carbon nanosphere after acid treatment are obviously increased, and the increase of the specific surface area is mainly caused by the formation of pores and holes.
(2)Fe2O3Preparation of @ C
13g of ferric nitrate was added to 100ml of anhydrous ethanol to prepare an alcoholic solution of ferric nitrate. And (2) adding the hollow carbon nanospheres prepared in the step (1) into an alcoholic solution of ferric nitrate, carrying out ultrasonic treatment for 0.5h, and then putting the mixture into a vacuum oven to be pumped to-0.1 Pa (25 ℃) by using a vacuum pump. Keeping the mixture for 1h under a vacuum condition, taking out the mixture, centrifugally washing the mixture, and transferring the mixture to a blast oven for drying for 12h at the temperature of 80 ℃. Repeatedly vacuum pumping and filling for 2-3 times, and marking the obtained material as Fe (NO)3)3@C。
Mixing Fe (NO)3)3@ C is put in a tube furnace, is heated to 200 ℃ at the heating rate of 2 ℃/min under the protection of nitrogen, and is kept at 200 DEG CCooling to room temperature for 2h, taking out to obtain black powder marked as Fe2O3@C。
Fe2O3The transmission electron micrograph and the element distribution chart of @ C are shown in FIG. 4. FIG. 4 is a transmission electron micrograph showing Fe2O3@ C has a core-shell structure, and nanoparticles are wrapped inside the hollow carbon nanospheres. While Fe is known from the element distribution2O3@ C is a carbon-coated iron oxide composite. While FIG. 2 reflects Fe2O3The mesoporous of the @ C hollow carbon nanosphere is filled, and the analysis of the nitrogen adsorption-desorption curve of FIG. 3 shows that Fe2O3@ C specific surface area 174.05m2V, pore volume 0.27cm3(ii) in terms of/g. By comparing the hollow carbon nanoball with Fe2O3The results of the test at @ C revealed that Fe was charged2O3The specific surface area and the total pore volume are obviously reduced, which shows that Fe2O3Successfully loaded into a carbon shell.
Comparative example
Adding 13g of ferric nitrate into 100ml of absolute ethyl alcohol to prepare an alcoholic solution of the ferric nitrate, then adding 2g of acetylene black into the alcoholic solution of the ferric nitrate, carrying out ultrasonic treatment for 0.5h, and then putting the mixture into a vacuum oven to be pumped to-0.1 Pa by using a vacuum pump. Keeping the mixture for 1h under a vacuum condition, taking out the mixture, centrifugally washing the mixture, and transferring the mixture to a blast oven for drying for 12h at the temperature of 80 ℃. Repeatedly vacuum pumping and filling for 2-3 times, placing in a tube furnace, heating to 200 deg.C at a heating rate of 2 deg.C/min under protection of nitrogen, maintaining at 200 deg.C for 2 hr, cooling to room temperature, taking out to obtain black powder, and marking as Fe2O3。
Electrochemical performance test
Assembling the button cell:
(1) according to Fe2O3@ C (examples): acetylene black: binder 8: 1: 1 to obtain slurry, uniformly coating the slurry on a copper foil current collector, drying after vacuum and pressing into a pole piece. In a glove box filled with argon (H)2O<0.1ppm，O2<0.1ppm), the prepared pole piece is taken as a research electrode (negative electrode), metal lithium is taken as a counter electrode, Celgard2400 is taken as a diaphragm, and 1mol/L LiPF6+EC+DMC(EC：The mass ratio of DMC is 1: 2) is used as electrolyte and is assembled into a button cell.
(2) Mixing Fe2O3(comparative example): acetylene black: binder 8: 1: 1 to obtain slurry, uniformly coating the slurry on a copper foil current collector, and drying and pressing the slurry into a pole piece. In a glove box filled with argon (H)2O<0.1ppm，O2<0.1ppm), the prepared pole piece is taken as a comparison electrode (negative electrode), metal lithium is taken as a counter electrode, Celgard2400 is taken as a diaphragm, and 1mol/L LiPF6And (4) assembling the button cell by taking the + EC + DMC (EC: DMC mass ratio is 1: 2) as electrolyte.
And (3) carrying out performance test on the prepared button cell under the following test conditions: at room temperature, the current density is 0.1A/g, 0.2A/g, 0.4A/g, 0.8A/g, 1.6A/g or 3.2A/g, and the voltage range is 0.01-3V. The method comprises the following specific steps:
(1) curve of charging and discharging
Fe2O3The typical electrostatic current charge-discharge curve test at 0.1A/g current of @ C is shown in FIG. 5, where Fe2O3The initial discharge capacity of the @ C electrode was 2149mAh/g, which is a high capacity due to decomposition of the electrolyte during formation of a solid electrolyte membrane (SEI film). In the following cycles, the charge and discharge curves tend to be consistent, indicating Fe2O3The @ C electrode has good electrochemical stability. By analysis, it is believed that Fe2O3The carbon coating shell of the @ C nano-particle is favorable for structural integrity to a certain extent, so that Fe2O3The @ C electrode has good electrochemical stability.
(2) Battery cycling stability test
The results of the charge and discharge tests were carried out at current densities of 0.1A/g, 0.2A/g, 0.4A/g, 0.8A/g, 1.6A/g, and 3.2A/g, as shown in FIG. 6. FIG. 6a shows that Fe2O3The initial discharge capacity of @ C under the high current density of 3.2A/g is 2149mAh/g, an inflection point is reached within 5 circles of circulation, the initial discharge capacity is 1515mAh/g, the capacity after 60 circles of circulation can still be kept at 519mAh/g, and the good circulation performance is realized, which can be attributed to that the carbon layer is used for Fe2O3Nano-limit effect, good conductivity of carbon layer and novel complete nano-meterStability of rice structure. The results of 100 cycles at 0.1A/g are shown in FIG. 6b, which shows Fe2O3The capacity remained 929mAh/g after 100 cycles of the @ C electrode. In contrast, Fe obtained by directly mixing acetylene black and ferric nitrate2O3After several cycles of the electrode, the initial charge capacity dropped sharply from 516.8mAh/g to 186.6 mAh/g. This continuous capacity loss is due to the crushing and active reduction caused by volume expansion/contraction. The test results further demonstrate that Fe is present due to the carbon coating2O3The @ C electrode has good cycling stability.
(3) And (3) rate performance test:
rate performance tests were performed on button cells at different current densities and the results are shown in fig. 7. Fe2O3The @ C electrode shows good rate performance, the capacity can be recovered to 1584.4mAh/g after the measurement is carried out under different current densities, and the @ C electrode has good reversibility and stable cycle performance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A metal oxide composite characterized by: the metal oxide composite material contains acetylene black hollow nanospheres, and metal oxides are packaged in the acetylene black hollow nanospheres.
2. The metal oxide composite material of claim 1, wherein: the metal oxide comprises Fe2O3、Fe3O4、Co3O4、CoO、NiO、TiO2Preferably Fe2O3。
3. The metal oxide composite material according to claim 2, wherein: the particle size of the acetylene black hollow nanospheres is 30-60 nm, and the aperture inside the acetylene black hollow nanospheres is 10-30 nm.
4. The metal oxide composite material according to any one of claims 1 to 3, wherein: the metal oxide is converted from metal salt encapsulated inside the acetylene black hollow nanosphere, and the mass ratio of the acetylene black hollow nanosphere to the metal salt is 1: 4-10, preferably 1: 5 to 8.
5. A method for producing the metal oxide composite material according to any one of claims 1 to 4, characterized in that: the method comprises the following steps: etching the acetylene black to obtain acetylene black hollow nanospheres; and encapsulating metal salt into the acetylene black hollow nanospheres, and calcining to obtain the metal oxide composite material.
6. The method according to claim 5, wherein: the etching method is acid etching; preferably, the acid etching method is to mix acetylene black with an oxidizing acid and react to obtain the acetylene black hollow nanospheres.
7. The method according to claim 6, wherein: the oxidizing acid comprises any one or more of concentrated nitric acid, concentrated sulfuric acid, permanganic acid and perchloric acid, and preferably concentrated nitric acid; the reaction temperature is 120-200 ℃, preferably 130-160 ℃.
8. The method according to claim 5, wherein: the method for encapsulating the metal salt into the acetylene black hollow nanospheres comprises the steps of mixing the metal salt solution with the acetylene black hollow nanospheres, and keeping the mixture for a period of time under a vacuum condition.
9. The method according to claim 5, wherein: the calcining temperature is 150-300 ℃.
10. Use of the metal oxide composite material according to any one of claims 1 to 4 for the preparation of an electrode or a lithium battery.
CN202110627162.8A 2021-06-04 2021-06-04 Metal oxide composite material and preparation method and application thereof Pending CN113540456A (en)

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CN104891468A (en) * 2015-03-26 2015-09-09 中国科学院化学研究所 Single-layer and multi-layer hollow carbon nanospheres, and preparation and application thereof

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Application publication date: 20211022