CN107673412A - A kind of porous Co3O4 nanometer material and its preparation method and application - Google Patents
A kind of porous Co3O4 nanometer material and its preparation method and application Download PDFInfo
- Publication number
- CN107673412A CN107673412A CN201711152893.1A CN201711152893A CN107673412A CN 107673412 A CN107673412 A CN 107673412A CN 201711152893 A CN201711152893 A CN 201711152893A CN 107673412 A CN107673412 A CN 107673412A
- Authority
- CN
- China
- Prior art keywords
- particle
- nanometer material
- porous
- preparation
- carbon nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- 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
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- 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
- H01M4/48—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 provides a kind of porous Co3O4 nanometer material and preparation method thereof.Described porous Co3O4 nanometer material, it is characterised in that for the loose structure being made up of cobaltosic oxide nano particle.Preparation process of the present invention is simple, easily operated, and reaction condition is gentle, is not related to poisonous, inflammable and explosive medicine in course of reaction, and in the absence of hazards such as poisoning blasts, and the reaction time is shorter, is a kind of effective efficiently preparation method.
Description
Technical field
The invention belongs to transition metal chalcogen compound porous nanometer materials and its preparation field, more particularly to porous four oxygen
Change three cobalt nano materials and its preparation method and application.
Background technology
Nano material specifically refer in three dimensions at least it is one-dimensional in nano-scale (0.1~100nm) either
The material be made up of it as elementary cell.The 1980s mid-term, nano metal material Preliminary development success, afterwards in succession
There is the appearance such as Nanometer Semiconductor Films, nano ceramics, nano magnetic material and nano biological medical material.Nano-particle material is again
Referred to as ultramicro powder material, it is made up of nano-particle (nano particle).Nano-particle is also ultramicro powder, generally refers to
Particle of the size between 1~100nm, it is to be in the transitional region that cluster and macro object have a common boundary, from common on microcosmic
Such system both atypical microscopic system also atypical macrosystem, it is a kind of typical be situated between from the viewpoint of macroscopic view
Sight system, it has skin effect, small-size effect, macro quanta tunnel effect and Dielectric confinement effect.A series of this effect
Nanometer particle material should be result in fusing point, vapour pressure, optical property, chemical reactivity, magnetic, superconduction and plastic deformation etc. to be permitted
More physics and chemistry aspect all show special performance.It make nanoparticle and nano-solid present many unusual physics,
Chemical property nano particle namely ultramicron surface have been covered with step structure, and this structure represents the shakiness with high surface energy
Determine atom, this kind of atom is easily adsorbed with foreign atom and is bonded, while the active atomic of large surface is provided because of particle diameter diminution.
However, because size is small, its specific surface area is quite big, and surface energy is of a relatively high, so as to which nano particle is easily reunited, is formed
Aggregate not of uniform size, have a strong impact on its chemical property as lithium electricity electrode material.Therefore, distinct methods design is studied
Particle distribution is good, and the uniform nano-particle material of pattern has extremely wide application prospect, turns into nano-particle material neck
One of study hotspot in domain.
Cobaltosic oxide is a kind of typical transition metal chalcogenide, and its crystal structure is typical spinelle structure
Type, wherein O2-Make cubic close accumulation, Co2+Ion is four-coordination, is filled in tetrahedron space, Co3+Ion is hexa-coordinate, is filled out
Fill in octahedral interstices.At present, Co3O4One of most fast transition metal oxide energy and material of progress is turned into, reason exists
In Co3O4With following tempting unique advantage：A) raw material is easy to get, and synthesis is simple；B) there is superelevation as lithium cell negative pole material
Theoretical capacity, about 890mAh g-1；C) there is good environmental stability.Co3O4Unique crystal structure, excellent machinery
Stability and good chemical property make it before the new energy fields such as ultracapacitor, lithium battery have and compare and be widely applied
Scape.But Co3O4Particle size itself is larger, and volumetric expansion easily occurs during circulating battery, in general nano-scale
Co3O4Serious agglomeration easily occurs for particle, so as to seriously limit its application in the field for energy storage material.Therefore
Design distribution is good, pattern is homogeneous and Co with special construction3O4Nano material is extremely important.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of porous Co3O4 nanometer material and preparation method thereof
And application, this method is easily operated, and reaction condition is gentle, the porous Co3O4 nanometer material chemical property being prepared
It is excellent.
In order to solve the above-mentioned technical problem, the invention provides a kind of porous Co3O4 nanometer material, its feature to exist
In for the loose structure being made up of cobaltosic oxide nano particle.
Described cobaltosic oxide nano particle is evenly distributed, size uniformity.
Preferably, the size of described cobaltosic oxide nano particle is 30-50nm.
Present invention also offers the preparation method of above-mentioned porous Co3O4 nanometer material, it is characterised in that including：
Step 1：Template carbon nano-particle is added in solvent, ultrasonic disperse, obtains template carbon nano-particle dispersion liquid；
Step 2：Four acetate hydrate cobalt solid particles are added in the template carbon nano-particle dispersion liquid in step 1, surpassed
Sound dissolves four acetate hydrate cobalt solid particles, obtains the mixed dispersion liquid of cobalt salt solution and template carbon nano-particle, this is mixed
Close dispersion liquid to be placed in water heating kettle, seal, hydro-thermal reaction 10h~20h, obtain intermediate carbon/cobalt salt composite；
Step 3：The carbon of gained/cobalt salt composite is placed in tube furnace, in atmosphere calcination reaction, removes template carbon
Nano particle, while it is cobaltosic oxide to convert cobalt salt, obtains porous Co3O4 nanometer material.
Preferably, described template carbon nano-particle prepares to obtain using glucose hydro-thermal method.
Preferably, the preparation method of described template carbon nano-particle includes：DEXTROSE ANHYDROUS is weighed, is added to deionization
In water, borax is added, dissolving is complete, and gained mixed liquor is placed in into water heating kettle, and 5-10h, gained production are reacted at 150-200 DEG C
Thing is washed repeatedly repeatedly with ethanol and deionized water, is dried, is produced template carbon nano-particle.
It is highly preferred that described DEXTROSE ANHYDROUS and the weight ratio of borax are：1∶10-20.
It is highly preferred that described reaction temperature is 180 DEG C, reaction time 8h.
Preferably, described template carbon nano-particle size dimension (i.e. particle diameter) is 10~50nm, more preferably 50nm；It is molten
Agent is at least one of ethanol, ethylene glycol or deionized water；The template carbon nano-particle finally given dispersion liquid in a solvent
Concentration be 1~6.25mg/mL.
Preferably, the ultrasonic time in described step 1 is 1~3h, more preferably 2h.
Preferably, the ultrasonic time in described step 2 is 0.5~2h, more preferably 1h.
Preferably, the cobalt salt solution concentration in the step 2 in described step 2 is 1.33~4.01mol/L.
Preferably, four described acetate hydrate cobalt additions and the mass ratio of template carbon nano-particle are 2: 1~12.5:
1。
Preferably, described hydrothermal temperature is 120 DEG C~170 DEG C, and more preferably 120 DEG C, the hydro-thermal time is 10~20h,
More preferably 12h.
Preferably, described carbon/cobalt salt composite calcining heat in tube furnace is 400 DEG C~800 DEG C, more preferably
500 DEG C~600 DEG C, calcination time is 2~6h, more preferably 4h.
Preferably, described porous Co3O4 nanometer material is preparing high-performance super capacitor electrode material or lithium
Application in ion battery electrode materials.
Porous Co3O4 nanometer material provided by the present invention, it is that gained carbon nanometer is prepared using glucose hydro-thermal method
Particle is template, and with four acetate hydrate cobalts by hydro-thermal reaction, further calcining is prepared in tube furnace；Its preparing raw material
Composition includes：Glucose, borax, four acetate hydrate cobalts, ethylene glycol, absolute ethyl alcohol and deionized water.Preparation method includes：It is logical
It is that catalyst progress hydro-thermal obtains template carbon nano-particle to cross glucose addition borax；Received by four acetate hydrate cobalts with template carbon
Rice grain hydro-thermal reaction, further tube furnace calcining remove template carbon nano-particle and generate final product cobaltosic oxide.
Porous Co3O4 nanometer material is prepared by simple technological design in the present invention；The nano material has
It is advantageous：It is catalyst by adding borax, the template carbon nano-particle appearance and size that G/W hot preparation obtains is homogeneous, point
Dissipate good, particle surface contains abundant oxygen-containing functional group, can be very good adsorbing metal cobalt ions, then by hydro-thermal reaction from
And carbon nano-particle and cobalt salt composite are formed well.Pass through air atmosphere calcination process, template carbon particle and oxygen again
Reaction generation carbon dioxide so as to be removed, meanwhile, cobalt salt is calcined in atmosphere to be converted into cobaltosic oxide with oxygen reaction and receives
Rice grain, the nano-cobaltic-cobaltous oxide product remain the appearance structure of template carbon, have very uniform appearance and size, particle
Distribution is good, and has loose structure, effectively inhibits the agglomeration of nano particle.Make it have very high ratio surface
Product, can the sufficiently contact with electrolyte and good reaction.Meanwhile loose structure effectively prevent the materials application in
Volumetric expansion and cave in phenomenon of the lithium cell cathode material in charge and discharge process, so that the high energy storage of cobaltosic oxide
Matter is played well.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) preparation process of the present invention is simple, easily operated, and reaction condition is gentle, be not related in course of reaction it is poisonous, it is inflammable
Explosive medicine, in the absence of hazards such as poisoning blasts, and the reaction time is shorter, is a kind of effective efficiently preparation method；
(2) present invention contains abundant oxygen-containing function by simple G/W thermal process, convenient effective prepared
Roll into a ball and appearance and size is homogeneous, well-distributed carbon nano-particle, its unique composition and structure can provide very big ratio surface
Product, and well with metallic cobalt ions binding, in this, as the template of compound cobalt salt, it can provide enough surface sites
To the combination of cobalt ions, and pass through water-heat process again, can be very good to form carbon/cobalt salt composite；
(3) introducing of loose structure effectively raises Co3O4 nanometer material specific surface area in the present invention, improves
Its chemical property as lithium cell negative pole material, while prevent its volume in charge and discharge process to a certain extent
Expand and cave in phenomenon；
(4) porous Co3O4 nanometer material prepared by the present invention has nanoscale structures, has higher ratio surface
Product, higher specific capacity value and preferable cyclical stability, are the new energy devices such as high-performance super capacitor, lithium ion battery
Preferable excellent materials.
Brief description of the drawings
Fig. 1 is the SEM of template carbon nano-particle in embodiment 1.
Fig. 2 is SEM and the TEM figure of porous Co3O4 nanometer material in embodiment 1.Wherein (a) SEM schemes, (b) TEM
Figure；
Fig. 3 is the XRD of porous Co3O4 nanometer material in embodiment 1；
Fig. 4 be in embodiment 1 porous Co3O4 nanometer material as lithium ion battery negative material in the big electricity of 1A/g
The cycle performance figure obtained under current density.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
A kind of porous Co3O4 nanometer material, for the loose structure being made up of cobaltosic oxide nano particle.It is described
Cobaltosic oxide nano particle be evenly distributed, size uniformity.
The preparation method of above-mentioned porous Co3O4 nanometer material, is concretely comprised the following steps：
(1) template carbon nano-particle is prepared using glucose hydro-thermal method, concretely comprised the following steps：35mg DEXTROSE ANHYDROUSs are weighed,
It is added in 80mL deionized waters, adds 535mg boraxs, dissolving is complete, and gained mixed liquor is placed in into 100mL water heating kettles,
8h is reacted at 180 DEG C, products therefrom is washed repeatedly repeatedly with ethanol and deionized water, is dried, is produced template carbon nano-particle.
Template carbon nano-particle size dimension is 50nm, and 80mg template carbon nano-particles are added in 80mL ethylene glycol,
It is scattered 2 hours with experiment supersonic cleaning machine continuous ultrasound, obtain template carbon nano-particle stable and uniform dispersion liquid；
(2) the acetate hydrate cobalt solid particles of 1000mg tetra- are weighed, are added in uniform dispersion obtained by step (1), room temperature
Lower ultrasonic 1h dissolves four acetate hydrate cobalt solid particles, obtains the mixed dispersion liquid of cobalt salt solution and template carbon nano-particle；
(3) gained mixed dispersion liquid in step (2) is poured into 100mL polytetrafluoroethyllining linings, is placed in reactor and seals,
120 DEG C of baking ovens are placed in, hydro-thermal reaction 12h, are cleaned repeatedly repeatedly with deionized water and ethanol, dries, obtains intermediate product carbon/cobalt salt
Composite；
(4) dried carbon/cobalt salt composite is placed in tube furnace, in the lower 500 DEG C of calcination reaction 4h of air atmosphere,
Template carbon nano-particle is removed, while it is cobaltosic oxide to convert cobalt salt, finally gives porous Co3O4 nanometer material, note
For PorousCo3O4。
Characterized using transmission electron microscope (TEM), SEM (SEM), X-ray diffractometer (XRD)
State template carbon nano-particle and final products therefrom Porous Co3O4The structure and morphology of nano material, its result are as follows：
(1) SEM test results show successfully to be prepared that pattern is good, and size dimension is homogeneous by glucose hydro-thermal method
And the template carbon nano-particle being evenly distributed, its particle size are about 50nm；Referring to Fig. 1.
(2) SEM and TEM test result shows：The complete replication master plate carbon of the porous Co3O4 nanometer material of gained
The pattern of nano particle, the particle for being about 30~50nm by size form, and size dimension is evenly distributed, and from SEM
It can also be observed that resulting materials have porous structure, the reunion of cobaltosic oxide nano particle is effectively prevented so that
Material integrally has very high specific surface area, and this unique structure can provide preferable stability, meanwhile, Co3O4Material sheet
Body has higher theoretical specific capacity, is the ideal electrode material for preparing the new energy devices such as ultracapacitor, lithium ion battery；
Referring to Fig. 2 (a) and (b).
(3) XRD test results show, porous Co3O4 nanometer material is in 2 θ=18.79,31.39,36.62,
38.44,44.73,55.58,59.33,65.23°The diffraction maximum with the presence of corresponding to, with cobaltosic oxide standard card PDF#42-
1467 is completely corresponding, and its corresponding crystal face is respectively (111), (220), (311), (222), (400), (422), (511),
(440).Prove successfully to prepare porous Co3O4 nanometer material；Referring to Fig. 3.
(4) electricity of porous Co3O4 nanometer material obtained above is characterized by assembling the button cells of CR 2025
Chemical property, its result are as follows：Under 1A/g high current densities, first circle discharge capacity is 1361.5mAh g-1, discharge and recharge ten encloses
It is reduced to 609.5mAh g-1, about 550mAh g are maintained essentially in afterwards-1Left and right, this shows this porous C o3O4Nano material is made
Being used for lithium ion battery negative material has good cycle performance and higher specific capacity；Referring to Fig. 4.
Embodiment 2
A kind of porous Co3O4 nanometer material, for the loose structure being made up of cobaltosic oxide nano particle.It is described
Cobaltosic oxide nano particle be evenly distributed, size uniformity.
The preparation method of above-mentioned porous Co3O4 nanometer material, is concretely comprised the following steps：
(1) template carbon nano-particle is prepared using glucose hydro-thermal method, concretely comprised the following steps：35mg DEXTROSE ANHYDROUSs are weighed,
It is added in 80mL deionized waters, adds 535mg boraxs, dissolving is complete, and gained mixed liquor is placed in into 100mL water heating kettles,
8h is reacted at 180 DEG C, products therefrom is washed repeatedly repeatedly with ethanol and deionized water, is dried, is produced template carbon nano-particle.
Template carbon nano-particle size dimension is 50nm, and 160mg template carbon nano-particles are added in 80mL ethylene glycol,
It is scattered 2 hours with experiment supersonic cleaning machine continuous ultrasound, obtain template carbon nano-particle stable and uniform dispersion liquid；
(2) the acetate hydrate cobalt solid particles of 332mg tetra- are weighed, are added in uniform dispersion obtained by step (1), at room temperature
Ultrasonic 1h dissolves four acetate hydrate cobalt solid particles, obtains the mixed dispersion liquid of cobalt salt solution and template carbon nano-particle；
(3) gained mixed dispersion liquid in step (2) is poured into 100mL polytetrafluoroethyllining linings, is placed in reactor and seals,
120 DEG C of baking ovens are placed in, hydro-thermal reaction 12h, are cleaned repeatedly repeatedly with deionized water and ethanol, dries, obtains intermediate product carbon/cobalt salt
Composite；
(4) dried carbon/cobalt salt composite is placed in tube furnace, in the lower 500 DEG C of calcination reaction 4h of air atmosphere,
Template carbon nano-particle is removed, while it is cobaltosic oxide to convert cobalt salt, finally gives porous Co3O4 nanometer material (gas
Gel), it is designated as PorousCo3O4-1。
Embodiment 3
A kind of porous Co3O4 nanometer material, for the loose structure being made up of cobaltosic oxide nano particle.It is described
Cobaltosic oxide nano particle be evenly distributed, size uniformity.
The preparation method of above-mentioned porous Co3O4 nanometer material, is concretely comprised the following steps：
(1) template carbon nano-particle is prepared using glucose hydro-thermal method, concretely comprised the following steps：35mg DEXTROSE ANHYDROUSs are weighed,
It is added in 80mL deionized waters, adds 535mg boraxs, dissolving is complete, and gained mixed liquor is placed in into 100mL water heating kettles,
8h is reacted at 180 DEG C, products therefrom is washed repeatedly repeatedly with ethanol and deionized water, is dried, is produced template carbon nano-particle.
Template carbon nano-particle size dimension is 50nm, and 500mg template carbon nano-particles are added in 80mL ethylene glycol,
It is scattered 2 hours with experiment supersonic cleaning machine continuous ultrasound, obtain template carbon nano-particle stable and uniform dispersion liquid；
(2) the acetate hydrate cobalt solid particles of 1000mg tetra- are weighed, are added in uniform dispersion obtained by step (1), room temperature
Lower ultrasonic 1h dissolves four acetate hydrate cobalt solid particles, obtains the mixed dispersion liquid of cobalt salt solution and template carbon nano-particle；
(3) gained mixed dispersion liquid in step (2) is poured into 100mL polytetrafluoroethyllining linings, is placed in reactor and seals,
120 DEG C of baking ovens are placed in, hydro-thermal reaction 12h, are cleaned repeatedly repeatedly with deionized water and ethanol, dries, obtains intermediate product carbon/cobalt salt
Composite；
(4) dried carbon/cobalt salt composite is placed in tube furnace, in the lower 500 DEG C of calcination reaction 4h of air atmosphere,
Template carbon nano-particle is removed, while it is cobaltosic oxide to convert cobalt salt, finally gives porous Co3O4 nanometer material (gas
Gel), it is designated as PorousCo3O4-2。
Claims (10)
1. a kind of porous Co3O4 nanometer material, it is characterised in that porous to be made up of cobaltosic oxide nano particle
Structure.
2. porous Co3O4 nanometer material as claimed in claim 1, it is characterised in that described cobaltosic oxide nano
The size of particle is 30-50nm.
3. the preparation method of the porous Co3O4 nanometer material described in claim 1 or 2, it is characterised in that including：
Step 1：Template carbon nano-particle is added in solvent, ultrasonic disperse, obtains template carbon nano-particle dispersion liquid；
Step 2：Four acetate hydrate cobalt solid particles are added in the template carbon nano-particle dispersion liquid in step 1, ultrasound makes
Four acetate hydrate cobalt solid particles dissolve, and obtain the mixed dispersion liquid of cobalt salt solution and template carbon nano-particle, by the mixing point
Dispersion liquid is placed in water heating kettle, sealing, hydro-thermal reaction 10h~20h, obtains intermediate carbon/cobalt salt composite；
Step 3：The carbon of gained/cobalt salt composite is placed in tube furnace, in atmosphere calcination reaction, removes template carbon nanometer
Particle, while it is cobaltosic oxide to convert cobalt salt, obtains porous Co3O4 nanometer material.
4. the preparation method of porous Co3O4 nanometer material as claimed in claim 3, it is characterised in that described template
Carbon nano-particle prepares to obtain using glucose hydro-thermal method.
5. the preparation method of porous Co3O4 nanometer material as claimed in claim 3, it is characterised in that described template
Carbon nano-particle size dimension is 10~50nm；Solvent is at least one of ethanol, ethylene glycol or deionized water；Finally give
The concentration of template carbon nano-particle dispersion liquid in a solvent be 1~6.25mg/mL.
6. the preparation method of porous Co3O4 nanometer material as claimed in claim 3, it is characterised in that described step
Cobalt salt solution concentration in step 2 in 2 is 1.33~4.01mol/L.
7. the preparation method of porous Co3O4 nanometer material as claimed in claim 3, it is characterised in that four described water
The mass ratio for closing cobalt acetate addition and template carbon nano-particle is 2: 1~12.5: 1.
8. the preparation method of porous Co3O4 nanometer material as claimed in claim 3, it is characterised in that described hydro-thermal
Temperature is 120 DEG C~170 DEG C, and the hydro-thermal time is 10~20h.
9. the preparation method of porous Co3O4 nanometer material as claimed in claim 3, it is characterised in that described carbon/
Cobalt salt composite calcining heat in tube furnace is 400 DEG C~800 DEG C, and calcination time is 2~6h.
10. the porous Co3O4 nanometer material described in claim 1 or 2 is preparing high-performance super capacitor electrode material
Or the application in lithium ion battery electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711152893.1A CN107673412A (en) | 2017-11-17 | 2017-11-17 | A kind of porous Co3O4 nanometer material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711152893.1A CN107673412A (en) | 2017-11-17 | 2017-11-17 | A kind of porous Co3O4 nanometer material and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107673412A true CN107673412A (en) | 2018-02-09 |
Family
ID=61148900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711152893.1A Pending CN107673412A (en) | 2017-11-17 | 2017-11-17 | A kind of porous Co3O4 nanometer material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107673412A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108538615A (en) * | 2018-05-21 | 2018-09-14 | 合肥仁德电子科技有限公司 | A kind of preparation method of cobaltosic oxide-Rare Earth Mine composite material |
| CN109292832A (en) * | 2018-12-07 | 2019-02-01 | 东华大学 | A kind of airsetting glue transition metal oxide material of size adjustable and preparation method thereof |
| CN109437328A (en) * | 2018-08-28 | 2019-03-08 | 五邑大学 | Preparation method of nano-scale short rod-shaped porous cobaltosic oxide electrode material |
| CN109546125A (en) * | 2018-11-23 | 2019-03-29 | 安徽工业大学 | A kind of preparation method of the porous mangaic acid magnesium positive electrode of spherical hollow |
| CN109786695A (en) * | 2018-12-29 | 2019-05-21 | 合肥融捷能源材料有限公司 | A kind of high magnification nickel-cobalt lithium manganate cathode material and preparation method thereof |
| CN109806872A (en) * | 2019-03-12 | 2019-05-28 | 东华大学 | A kind of application of three-dimensional carbon doped cobaltic-cobaltous oxide material |
| CN110683589A (en) * | 2019-10-17 | 2020-01-14 | 宁波大学 | Preparation method of cobaltosic oxide nano material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464304A (en) * | 2010-11-12 | 2012-05-23 | 中国科学院过程工程研究所 | Multi-shell-layer metal oxide hollow ball and preparation method thereof |
| CN103011306A (en) * | 2013-01-04 | 2013-04-03 | 南京工业大学 | Method for preparing nanometer-level cube-like cobaltosic oxide |
| CN103803664A (en) * | 2012-11-14 | 2014-05-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of tricobalt tetroxide cored nano hollow spheres |
| CN106006761A (en) * | 2016-06-29 | 2016-10-12 | 渤海大学 | Preparation method of cobaltosic oxide hierarchic structure material |
| CN106348349A (en) * | 2016-08-26 | 2017-01-25 | 内江师范学院 | Cobaltosic oxide with large specific surface area and hollow structure as well as synthesis method and application thereof |
-
2017
- 2017-11-17 CN CN201711152893.1A patent/CN107673412A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464304A (en) * | 2010-11-12 | 2012-05-23 | 中国科学院过程工程研究所 | Multi-shell-layer metal oxide hollow ball and preparation method thereof |
| CN103803664A (en) * | 2012-11-14 | 2014-05-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of tricobalt tetroxide cored nano hollow spheres |
| CN103011306A (en) * | 2013-01-04 | 2013-04-03 | 南京工业大学 | Method for preparing nanometer-level cube-like cobaltosic oxide |
| CN106006761A (en) * | 2016-06-29 | 2016-10-12 | 渤海大学 | Preparation method of cobaltosic oxide hierarchic structure material |
| CN106348349A (en) * | 2016-08-26 | 2017-01-25 | 内江师范学院 | Cobaltosic oxide with large specific surface area and hollow structure as well as synthesis method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| WEIWEI ZHAO等: "Preparation and characterization of hollow Co3O4 spheres", 《MATERIALS LETTERS》 * |
| 卿小霞等: "以胶体碳球为模板剂合成纳米四氧化三钴空心球", 《化学工程与装备》 * |
| 王习文: "纳米四氧化三钴系化合物的合成及其超级电容性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108538615A (en) * | 2018-05-21 | 2018-09-14 | 合肥仁德电子科技有限公司 | A kind of preparation method of cobaltosic oxide-Rare Earth Mine composite material |
| CN108538615B (en) * | 2018-05-21 | 2021-05-14 | 江西联锴新材料有限公司 | Preparation method of cobaltosic oxide-rare earth ore composite material |
| CN109437328A (en) * | 2018-08-28 | 2019-03-08 | 五邑大学 | Preparation method of nano-scale short rod-shaped porous cobaltosic oxide electrode material |
| CN109546125A (en) * | 2018-11-23 | 2019-03-29 | 安徽工业大学 | A kind of preparation method of the porous mangaic acid magnesium positive electrode of spherical hollow |
| CN109292832A (en) * | 2018-12-07 | 2019-02-01 | 东华大学 | A kind of airsetting glue transition metal oxide material of size adjustable and preparation method thereof |
| CN109786695A (en) * | 2018-12-29 | 2019-05-21 | 合肥融捷能源材料有限公司 | A kind of high magnification nickel-cobalt lithium manganate cathode material and preparation method thereof |
| CN109786695B (en) * | 2018-12-29 | 2022-01-28 | 合肥融捷能源材料有限公司 | High-rate lithium nickel cobalt manganese oxide positive electrode material and preparation method thereof |
| CN109806872A (en) * | 2019-03-12 | 2019-05-28 | 东华大学 | A kind of application of three-dimensional carbon doped cobaltic-cobaltous oxide material |
| CN110683589A (en) * | 2019-10-17 | 2020-01-14 | 宁波大学 | Preparation method of cobaltosic oxide nano material |
| CN110683589B (en) * | 2019-10-17 | 2022-03-25 | 宁波大学 | Preparation method of cobaltosic oxide nano material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107673412A (en) | A kind of porous Co3O4 nanometer material and its preparation method and application | |
| Hou et al. | Hollow dodecahedral Co3S4@ NiO derived from ZIF-67 for supercapacitor | |
| Ding et al. | Design of multishell microsphere of transition metal oxides/carbon composites for lithium ion battery | |
| Hussain et al. | Robust TiN nanoparticles polysulfide anchor for Li–S storage and diffusion pathways using first principle calculations | |
| CN108711611B (en) | Three-dimensional high-density metal nanoparticle/graphene porous composite material and preparation method and application thereof | |
| Park et al. | Effect of esterification reaction of citric acid and ethylene glycol on the formation of multi-shelled cobalt oxide powders with superior electrochemical properties | |
| CN108390014A (en) | The preparation method of foamed nickel supported different-shape cobalt black nano material | |
| CN106450219B (en) | A kind of three-dimensional vanadium trioxide/carbon composite nano-material and its preparation method and application of various dimensions assembling | |
| Cong et al. | Metal–organic framework derived amorphous VO x coated Fe 3 O 4/C hierarchical nanospindle as anode material for superior lithium-ion batteries | |
| Feng et al. | Carbon-coated Fe 2 O 3 hollow sea urchin nanostructures as high-performance anode materials for lithium-ion battery | |
| CN100459279C (en) | Magnesium negative material and preparation method and application | |
| Li et al. | Microwave-assisted synthesis of the sandwich-like porous Al2O3/RGO nanosheets anchoring NiO nanocomposite as anode materials for lithium-ion batteries | |
| CN104860349B (en) | Titanium dioxide hollow ball that a kind of nanometer rods are constructed and preparation method and application | |
| CN106025240A (en) | Preparation method of C/SnO2/CNT (carbon nano tube) composite material of core shell structure for lithium ion battery cathode | |
| CN109473643B (en) | CoSe2Preparation method and application of graphene composite material | |
| CN107611359A (en) | The preparation method of lithium ion battery Ni NiO/ graphene composite negative poles | |
| Zhang et al. | A novel SnS2 nanomaterial based on nitrogen-doped cubic-like carbon skeleton with excellent lithium storage | |
| CN106953079B (en) | A kind of multilevel structure carbon nano tube/tin dioxide composite material and preparation method | |
| Zhang et al. | Synthesis of Mn-doped α-Ni (OH) 2 nanosheets assisted by liquid-phase laser ablation and their electrochemical properties | |
| Guo et al. | Nanosheets-in-nanotube Co3O4-carbon array design enables stable Li-ion storage | |
| Nie et al. | Using Prussian blue as a self-sacrificial template to construct MnO/MnFe2O4 microcubes as anodes for lithium-ion batteries | |
| CN109671574B (en) | MnCo2O4Nano-spherical particles, preparation method thereof and application thereof in super capacitor | |
| Zhang et al. | Synthesizing Cu-doped CoSe2 nanoframe cubics for Na-ion batteries electrodes | |
| Zhao et al. | Facile fabrication of hollow CuO nanocubes for enhanced lithium/sodium storage performance | |
| CN108963237B (en) | Preparation method of sodium ion battery negative electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180209 |