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
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- 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
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000011852 carbon nanoparticle Substances 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 25
- 239000006185 dispersion Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 150000001868 cobalt Chemical class 0.000 claims description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- GDUDPOLSCZNKMK-UHFFFAOYSA-L cobalt(2+);diacetate;hydrate Chemical compound O.[Co+2].CC([O-])=O.CC([O-])=O GDUDPOLSCZNKMK-UHFFFAOYSA-L 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 150000001721 carbon Chemical class 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 7
- 239000007772 electrode material Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 239000003990 capacitor Substances 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 239000002360 explosive Substances 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- 231100000572 poisoning Toxicity 0.000 abstract description 2
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 230000007096 poisonous effect Effects 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 235000010339 sodium tetraborate Nutrition 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910021538 borax Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004328 sodium tetraborate Substances 0.000 description 5
- 235000013495 cobalt Nutrition 0.000 description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- 239000013078 crystal Chemical group 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000008121 dextrose Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 transition metal chalcogen compound Chemical class 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 206010044565 Tremor Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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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- H01G11/46—Metal oxides
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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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.
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