CN108212035A - A kind of porous core-shell nano composite material and preparation method thereof - Google Patents

A kind of porous core-shell nano composite material and preparation method thereof Download PDF

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Publication number
CN108212035A
CN108212035A CN201711346046.9A CN201711346046A CN108212035A CN 108212035 A CN108212035 A CN 108212035A CN 201711346046 A CN201711346046 A CN 201711346046A CN 108212035 A CN108212035 A CN 108212035A
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mxoy
preparation
metal
shell
porous
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徐冬阳
谢墨
尹华歧
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Chengdu Yinlong New Energy Co Ltd
Yinlong New Energy Co Ltd
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Chengdu Yinlong New Energy Co Ltd
Yinlong New Energy Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B01J13/043—Drying and spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/74—Iron group metals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B01J35/33—
    • B01J35/398—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • 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
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Abstract

The present invention relates to a kind of porous core-shell nano composite material and preparation methods, the porous core-shell nano composite material is the MxOy@C of controllable appearance size, porous carbon nanostructured shell is uniformly wrapped on MxOy nano grain surfaces, described porous carbon nano-structured for carbon nanosheet, nanometer blocks or nanosphere；M is selected from any one of Co, Ni metal, when M is Co, x=3, y=4；When M is Ni, x=1, y=1.Its preparation includes the following steps：By soluble M metal salt, glucose and sodium chloride co-dissolve；Dope is formed after stirring, heating；Through drying, grinding, the M metal salt glucose compound crystal powder of sodium chloride cladding is obtained；Through being calcined under argon atmosphere, oxidation obtains porous carbon-coated M metal oxides nucleocapsid composite material in air.Its preparation process is simple, technique is easy to control, suitable for industrial volume production, prepares product available for multiple uses such as electrode material, catalyst material, super capacitor materials.

Description

A kind of porous core-shell nano composite material and preparation method thereof
Technical field
The present invention relates to field of nanocomposite materials, especially core-shell nano field of compound material, and in particular to Yi Zhongduo Hole core-shell nano composite material and preparation method thereof.
Background technology
With the fast development of carbon nanomaterial, porous carbon nanomaterial is because there are a large amount of hole, big specific surface areas With unique framework composition the great interest of researchers has been caused in a variety of different fields.In recent years, porous carbon Nano material is widely used in electrochemical field, is used for example as the catalyst of electro-catalysis and the electrode material of capacitor Deng.Common molte-salt synthesis prepares porous carbon nanomaterial, compared with hydro-thermal carbon nano material, carbonizing degree higher, still It can only obtain the graphite material of big sheet under many treatment conditions, hardly result in the porous carbon nanomaterial such as blocky, spherical.It is open It number discloses a kind of molte-salt synthesis for the patent of invention of CN104176765A and prepares different-shape ZnO nano material, can prepare Obtain short-term shape, needle-shaped, bamboo shoot shape and short cylinder ZnO nano material, product morphology is controllable and volume production, but technology controlling and process it is complicated, It is unsuitable for industrial volume production.
Metal oxide@porous carbon composites can be used as catalyst, Li ion batteries (LIBs) and super capacitor electrode Pole material etc. has a very big application potential in field of energy environment, but the preparation processes such as template-activation method common at present it is complicated, How poor controllability, the industrial volume production that is unsuitable for, develop a kind of preparation method, it is simple, can volume production, can be to metal oxide@ The pattern and size of carbon composite are controlled, and are to have technical barrier to be solved at present so as to extend its performance.
Invention content
In view of above-mentioned technical problem, the present invention provides a kind of metal oxide@porous carbon composites and its preparation sides Method, raw material is cheap, preparation process is simple, technique is easy to control, suitable for industrial volume production, prepares product available for electrode material The multiple uses such as material, catalyst material, super capacitor material.
The present invention provides a kind of porous core-shell nano composite materials of MxOy C, porous carbon nanostructured shell uniformly coats It is described carbon nano-structured for carbon nanosheet, nanometer blocks or nanosphere in MxOy nano grain surfaces；M is appointing in Co, Ni A kind of metal, when M is Co, x=3, y=4；When M is Ni, x=1, y=1.
Preferably, the porous core-shell nano composite materials of MxOy@C are the nanometer sheet of 200~400nm of average grain diameter.
Preferably, the porous core-shell nano composite materials of MxOy@C are the nanometer blocks of average grain diameter 100-150nm.
Preferably, the porous core-shell nano composite materials of MxOy@C are the nanosphere of average grain diameter 30-100nm.
Further, the thickness of the porous carbon nanostructured shell is 20-100nm.
The present invention also provides the preparation methods of the porous core-shell nano composite materials of MxOy@C, include the following steps：
(1) soluble M metal salt, glucose and sodium chloride co-dissolve are obtained into uniform mixing in water, after stirring Solution；
(2) dope is formed after heating；Preferably, heating makes glucose denaturation increase viscosity complexing M metal ions, later Constant temperature stirring, evaporation solution, until solution colour deepens blackening, stop stirring, continue to be heated to solution in thick；
(3) dope for obtaining step (2) is dried, and obtains M metal salts-glucose composite junction crystalline flour of sodium chloride cladding Then end is ground；
(4) ground compound crystal powder is calcined under an argon, M metal salts are decomposed to form M metal oxides, Portugal The M metal oxides are reduced into M metal nanoparticles, and receive in M metals by the carbon that grape sugar is pyrolyzed under high temperature argon protection The porous carbon nano-structured of uniform thickness is formed around rice grain；
(5) nanostructured that step (4) obtains is calcined in air, the MxOy of porous carbon structure cladding is obtained after oxidation Nano particle composite material.
Wherein, it is 1 by controlling the mass ratio of the soluble M metal salt and glucose:2-2:1, obtain different-shape, The porous core-shell nano composite materials of MxOy@C of size.
Further, in the mixed solution described in step (1), the mass concentration of sodium chloride is 10-20%.
Further, step (2) described constant temperature is 60-95 DEG C, and magnetic agitation simultaneously evaporates solution 2-6 hours.
Further, step (3) described drying is 12-24 hours dry in 60-95 DEG C of drying box.
Further, step (4) is specially：Ground compound crystal powder is transferred in vacuum tube furnace, in 450- 750 DEG C, under argon atmospher, flow velocity 50-200mL/min is calcined 2-4 hours, and M metal salts are decomposed to form M metal oxides, from Portugal M oxide is reduced into M metal nanoparticles by the carbon of grape sugar, and uniform thickness 20- is formed around M metal nanoparticles 100nm's is porous carbon nano-structured；As preference, it is calcined 2 hours at 750 DEG C of temperature.
Further, step (5) is specially：The nanostructured that step (4) is obtained is calcined at 200-350 DEG C in air 4-12 hours, the MxOy nano particle composite materials of porous carbon structure cladding are obtained after oxidation.
Compared with prior art, the present invention has following advantageous effect：
(1) it by controlling the mass ratio of presoma metal salt and glucose, realizes microcosmic to nano-core-shell structure material The simple and effective control of pattern and size, raw material is cheap, preparation process is simple, easy control of process conditions, to environment friend Well, suitable for industrial volume production.
(2) pattern and size for the MxOy nano particle composite materials that product-porous carbon structure coats are prepared by adjusting, Application of the material in terms of electrochemistry, the wherein Co of 50~100nm of grain size are expanded3O4@C nano balls, for the first time discharge capacity Reach more than 1290mAh/g, after 500 charge and discharge, specific capacity still reaches 450mAh/g, capacitance reach 440F/g with On, catalytic polarization curve is 142mAcm-2So that composite material chemical property significantly improves, and available for electrode material, surpasses Grade capacitance material, catalyst etc..
Description of the drawings
Fig. 1 is 1Co of the embodiment of the present invention3O4The preparation method flow diagram of the porous core-shell nano composite materials of@C；
Fig. 2 is the Co that the embodiment of the present invention 1 is prepared3O4The microstructure of the porous core-shell nano composite materials of@C；
Wherein：
Fig. 2 a are Co3O4The SEM figures of the porous core-shell nano laminated structures of@C-1；
Fig. 2 b are Co3O4The SEM figures of the porous core-shell nano block structures of@C-2；
Fig. 2 c are Co3O4The SEM figures of the spherical structure of the porous core-shell nanos of@C-3；
Fig. 2 d are Co3O4The TEM figures of the porous core-shell nano laminated structures of@C-1；
Fig. 2 e are Co3O4The TEM figures of the porous core-shell nano block structures of@C-2；
Fig. 2 f are Co3O4The TEM figures of the spherical structure of the porous core-shell nanos of@C-3；
Fig. 3 is the microstructure of the porous core-shell nano composite materials of NiO@C that the embodiment of the present invention 2 is prepared；
Wherein：
Fig. 3 a are that the SEM of the porous core-shell nano laminated structures of NiO@C-1 schemes；
Fig. 3 b are that the SEM of the porous core-shell nano block structures of NiO@C-2 schemes；
Fig. 3 c are that the SEM of the spherical structure of the porous core-shell nanos of NiO C-3 schemes；
Fig. 3 d are that the TEM of the porous core-shell nano laminated structures of NiO@C-1 schemes；
Fig. 3 e are that the TEM of the porous core-shell nano block structures of NiO@C-2 schemes；
Fig. 3 f are that the TEM of the spherical structure of the porous core-shell nanos of NiO C-3 schemes；
Fig. 4 is the preparation process schematic diagram of the porous core-shell nano composite materials of MxOy@C of the present invention.
Specific embodiment
The preferred embodiment that the invention will now be described in detail with reference to the accompanying drawings.
Embodiment 1
A kind of Co3O4The preparation method of the porous core-shell nano composite materials of@C, includes the following steps：
(1) Co (NO are pressed respectively3)2·6H2O：Glucose quality ratio is 1:2、1:1、2:1 (corresponds to material in table 1 respectively Co3O4@C-1、Co3O4@C-2、Co3O4@C-3) and sodium chloride co-dissolve in deionized water, by mixed solution first in magnetic On power blender, heating stirring to no solid particle obtains red uniform solution, a concentration of 10-20% of Chlorine in Solution sodium；
(2) solution after stirring is first boiled 0.5 hour, allow glucose denaturation increase viscosity complexation of metal ions, after put Enter in 60-95 DEG C of temperature constant magnetic stirring water-bath, evaporation stirring in 2-6 hours, until solution treats solution face in kermesinus or black Discoloration depth blackening stops magnetic agitation, continues heating water bath to viscosity and increases, until when solution is in thick shape, takes out；
(3) obtained mixing dope is placed on drying 12-24 hours in 60-95 DEG C of drying box, obtains dry chlorine Change the Co (NO of sodium cladding3)2-C6H12O6Compound crystal powder, then grinds；
(4) compound crystal powder is transferred in vacuum tube furnace, under 450-750 DEG C, argon atmosphere, flow velocity 50- 200mL/min is calcined 2-4 hours, and preferably 750 DEG C are calcined 2 hours, metal precursor Co (NO3)2·6H2O is decomposed to form cobalt oxide, Cobalt oxide is reduced into cobalt nano-particle by the carbon from glucose, and encapsulation carbon-coating, Jin Er are formed on sodium chloride particle surface The porous carbon nano-structured of uniform thickness 20-100nm is formed around cobalt nano-particle；
(5) it will be calcined 4-12 hours at Co@C porous nanometer structures in air 250-350 DEG C, product obtained after oxidation, That is the cobalt/cobalt oxide nano particle composite material of porous carbon structure cladding.
The porous core-shell nano composite material is the Co of controllable appearance size3O4@C。
Show through SEM, tem analysis as shown in Fig. 2, obtaining final product Co3O4@C-1 nano-sheets (a, d), Co3O4@ C-2 nanometers of blocky (b, e), Co3O4C-3 nanometers of@spherical (c, f).
Electrochemical property test further is carried out to product, the results are shown in Table shown in 1, button electricity can be fabricated to by preparing product Pond, super capacitor, Electrochemical oxygen evolution catalyst etc..
1 Co of table3O4The electrochemical property test result of@C core-shell nano composite materials：
Embodiment 2
A kind of preparation method of the porous core-shell nano composite materials of NiO@C, includes the following steps：
(1) Ni (NO are pressed respectively3)2·6H2O：Glucose quality ratio is 1:2、1:1、2:1 (corresponds to material in table 2 respectively NiO@C-1, NiO@C-2, NiO@C-3) and sodium chloride co-dissolve in deionized water, mixed solution is first stirred in magnetic force It mixes on device, heating stirring to no solid particle, obtains green uniform solution, a concentration of 10-20% of Chlorine in Solution sodium；
(2) solution after stirring is first boiled 0.5 hour, allow glucose denaturation increase viscosity complexation of metal ions, after put Enter in 80-95 DEG C of temperature constant magnetic stirring water-bath, evaporation stirring in 2-6 hours until solution is in dark green or blackish green, treats solution face Discoloration depth blackening, stopping magnetic agitation continuing heating water bath to viscosity and increase, and without the uniform energy pull-up silk of bulky grain energy, moisture It is less in it is thick when, take out；
(3) obtained mixing dope is placed on drying 12-24 hours in 80-95 DEG C of drying box, obtains dry chlorine Change the Ni (NO of sodium cladding3)2-C6H12O6Compound crystal powder, then grinds；
(4) compound crystal powder is transferred in vacuum tube furnace, under 450-750 DEG C, argon atmosphere, flow velocity 50- 200mL/min is calcined 2-6 hours, and Ni oxides are reduced into Ni nanometers by pyrolytic carbon of the glucose under high temperature argon protection , encapsulation carbon-coating is formed on sodium chloride particle surface, and then the more of uniform thickness 20-100nm are formed around Ni nano particles Hole is carbon nano-structured；
(5) it will be calcined 4-12 hours at Ni@C nanometer nuclear shell nano-structures in air 200-300 DEG C, porous carbon obtained after oxidation The nickel oxide nano particle composite material of structure cladding.
The porous core-shell nano composite material is the NiO@C of controllable appearance size.
Show through SEM, tem analysis as shown in Fig. 2, obtaining final product NiO@C-1 nano-sheets (a, d), NiO@C-2 Nanometer blocky (b, e), C-3 nanometers of NiO spherical (c, f).
Electrochemical property test further is carried out to product, the results are shown in Table shown in 2, button electricity can be fabricated to by preparing product Pond, super capacitor, Electrochemical oxygen evolution catalyst etc..
The electrochemical property test result of 2 NiO@C core-shell nano composite materials of table：
What has been described above is only a preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art For, any modification, equivalent replacement, improvement and so on, should be included in without departing from the concept of the premise of the invention Within protection scope of the present invention.

Claims (15)

1. a kind of porous core-shell nano composite materials of MxOy@C, it is characterised in that：Porous carbon nanostructured shell is uniformly wrapped on MxOy nano grain surfaces, it is described carbon nano-structured for carbon nanosheet, nanometer blocks or nanosphere；M is any in Co, Ni Kind metal, when M is Co, x=3, y=4；When M is Ni, x=1, y=1.
2. nanocomposite according to claim 1, it is characterised in that：The porous core-shell nano composite woods of MxOy@C Expect the nanometer sheet for 200~400nm of average grain diameter.
3. nanocomposite according to claim 1, it is characterised in that：The porous core-shell nano composite woods of MxOy@C Expect the nanometer blocks for average grain diameter 100-150nm.
4. nanocomposite according to claim 1, it is characterised in that：The porous core-shell nano composite woods of MxOy@C Expect the nanosphere for average grain diameter 30-100nm.
5. according to any nanocomposites of claim 1-4, it is characterised in that：
The thickness of the porous carbon nanostructured shell is 20-100nm.
6. a kind of preparation method of any porous core-shell nano composite materials of MxOy@C of claim 1-5, including as follows Step：
(1) soluble M metal salt, glucose and sodium chloride co-dissolve are obtained into uniform mixed solution in water, after stirring；
(2) dope is formed after heating；
(3) dope for obtaining step (2) is dried, and obtains M metal salts-glucose compound crystal powder of sodium chloride cladding；
(4) ground compound crystal powder is calcined under argon atmosphere, M metal salts are decomposed to form M metal oxides, grape The M metal oxides are reduced into M metal nanoparticles, and in M metal nanos by the carbon that sugar is pyrolyzed under high temperature argon protection The porous carbon nano-structured of uniform thickness is formed around particle；
(5) nanostructured that step (4) obtains is calcined in air, the MxOy nanometers of porous carbon structure cladding is obtained after oxidation Particulate composite.
7. preparation method according to claim 6, it is characterised in that：By controlling the soluble M metal salt and grape The mass ratio of sugar is 1:2-2:1, obtain different-shape, size the porous core-shell nano composite materials of MxOy@C.
8. the preparation method described according to claim 6 or 7, it is characterised in that：In mixed solution described in step (1), chlorination The mass concentration of sodium is 10-20%.
9. the preparation method described according to claim 6 or 7, it is characterised in that：Dope is formed after step (2) heating to include： Heating makes glucose denaturation increase viscosity complexing M metal ions, stirs later, evaporates solution, until solution colour deepens blackening, Stop stirring, continue to be heated to solution in thick.
10. preparation method according to claim 9, it is characterised in that：Step (2) described constant temperature is 60-95 DEG C, and magnetic force stirs It mixes and evaporates solution 2-6 hours.
11. the preparation method described according to claim 6 or 7, it is characterised in that：Step (3) described drying is at 60-95 DEG C It is 12-24 hours dry in drying box.
12. the preparation method described according to claim 6 or 7, it is characterised in that：Step (4) is specially：It will be ground compound Crystalline powder is transferred in vacuum tube furnace, and under 450-750 DEG C, argon atmosphere, flow velocity 50-200mL/min is calcined 2-4 hours, M metal salts are decomposed to form M metal oxides, and M oxide is reduced into M metals by the carbon that glucose is pyrolyzed under high temperature argon protection Nano particle, and the porous carbon nano-structured of uniform thickness 20-100nm is formed around M metal nanoparticles.
13. preparation method according to claim 12, it is characterised in that：At 750 DEG C of temperature, calcine 2 hours.
14. the preparation method described according to claim 6 or 7, it is characterised in that：Step (5) is specially：Step (4) is obtained Nanostructured calcine 4-12 hours at 200-350 DEG C in air, the MxOy nanometers of porous carbon structure cladding are obtained after oxidation Particulate composite.
15. a kind of purposes of any porous core-shell nano composite materials of MxOy@C of claim 6-14, it is characterised in that：
For making electrode material, super capacitor or Electrochemical oxygen evolution catalyst.
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CN109437322A (en) * 2018-11-05 2019-03-08 浙江工业大学 A kind of compound carbon ball of metal oxide and preparation method thereof
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WO2021078113A1 (en) * 2019-10-21 2021-04-29 中国石油化工股份有限公司 Carbon-coated nickel-aluminum nanocomposite, preparation method therefor and application thereof
CN111508719A (en) * 2020-04-24 2020-08-07 陈志林 Carbon-coated Co with shell-core structure3O4Super capacitor electrode material and preparation method thereof
CN111504105A (en) * 2020-04-30 2020-08-07 北京工业大学 Liquid absorption core for heat pipe or vapor chamber formed by multiple phase pore-forming agent and manufacturing method thereof
CN111504105B (en) * 2020-04-30 2022-01-18 北京工业大学 Liquid absorption core for heat pipe or vapor chamber formed by multiple phase pore-forming agent and manufacturing method thereof
CN112259745B (en) * 2020-09-09 2023-01-17 温州大学新材料与产业技术研究院 Oxygen reduction electrocatalyst based on nitrogen and sulfur co-doped carbon microsphere/carbon sheet material and application thereof
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CN114685090A (en) * 2020-12-30 2022-07-01 博特新材料泰州有限公司 Controlled-release early-strength composite material, preparation method and application thereof in cement-based material
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