CN104167297B - A kind of mesoporous cobaltosic oxide of ultracapacitor tubulose and preparation method thereof - Google Patents
A kind of mesoporous cobaltosic oxide of ultracapacitor tubulose and preparation method thereof Download PDFInfo
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- CN104167297B CN104167297B CN201410424428.9A CN201410424428A CN104167297B CN 104167297 B CN104167297 B CN 104167297B CN 201410424428 A CN201410424428 A CN 201410424428A CN 104167297 B CN104167297 B CN 104167297B
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses a kind of mesoporous cobaltosic oxide of ultracapacitor tubulose and preparation method thereof.The mesoporous cobaltosic oxide of described tubulose prepares by template of cotton.The preparation method of the mesoporous cobaltosic oxide powder of described tubulose is that cotton is immersed in the aqueous solution of cobalt nitrate, calcines to obtain cobaltosic oxide powder in atmosphere by the cotton for adsorbing cobalt nitrate after to be dried.The mesoporous cobaltosic oxide aperture of described tubulose is 9 25 nm, caliber is 8 20 μm, boss ratio is more than the cobaltosic oxide that 1, draw ratio is more than 10.The mesoporous cobaltosic oxide of tubulose can be used as the electrode material of ultracapacitor because having good capacitance characteristic and higher energy storage characteristic.Compared with the existing technology, technique is simple, operates the advantages that easy, environmentally friendly, raw material sources are abundant, low cost and performance are good, suitable industrialized production by the present invention.
Description
Technical field
It is mesoporous more particularly, to a kind of ultracapacitor tubulose the present invention relates to a kind of electrode for super capacitor material
Cobaltosic oxide and preparation method thereof.
Background technology
Cobaltosic oxide is a kind of important functional material, be commonly used for lithium ion battery, ultracapacitor, sensor,
Catalysis etc..For cobaltosic oxide in the application of reality, its pattern has very big influence for its performance.Therefore, respectively
The cobaltosic oxide of kind pattern, such as flower-shaped, sheet, box-like, wire, tubulose have preparation, and have various applications.In these shapes
In the cobaltosic oxide of looks, because the cobaltosic oxide of one-dimensional tubulose is because it is with unique physical and chemical performance and by special
Concern.As Shi et al. using colloid bead as template is prepared for cobaltosic oxide nano-tube（Xiangyang Shi, Shubo
Han, Raymond J. Sanedrin, Cesar Galvez, David G. Ho, Billy Hernandex, Feimeng
Zhou, Matthias Selke. Formation of cobalt oxide nanotubes: Effect of
intermolecular hydrogen bonding between Co(III) complex precursors
incorporated onto colloidal templates [J]. Nano Letters, 2002, 2(4): 289-
293）；Chen et al. is prepared for tubulose cobaltosic oxide by template of porous aluminum（Weiyang Li, Lina Xu, Jun
Chen. Co3O4 nanomaterials in lithium-ion batteries and gas sensors [J].
Advanced Functional Materials, 2008, 15(5): 851-857）Deng.But these preparation methods are too multiple
It is miscellaneous, cost is high, and these preparation method feature of environmental protection are not strong, and the versatility of material is not strong.
The present invention uses natural cotton as template, develops tubulose cobaltosic oxide, and prepared tubulose four oxidation three
Cobalt also has mesoporous characteristic, this for improve its chemical property have the function that it is positive.
The content of the invention
The invention aims to overcome the shortcomings of prior art, there is provided a kind of technique is simple, it is easy, environmentally friendly to operate,
Mesoporous cobaltosic oxide of ultracapacitor tubulose that raw material sources are abundant, low cost and performance are good and preparation method thereof.
What the present invention was realized in：
A kind of mesoporous cobaltosic oxide of ultracapacitor tubulose, using cotton and cobalt nitrate hexahydrate as raw material, is prepared
The mesoporous cobaltosic oxide product of tubulose, its characteristic are：Aperture is 9-25nm, caliber is 8-20 μm, boss ratio is more than 1, major diameter
Than more than for 10.
A kind of preparation method of the mesoporous cobaltosic oxide of ultracapacitor tubulose, using cotton as template, with six water nitric acid
Cobalt is raw material, soaking, dry and calcination process, and the mesoporous cobaltosic oxide product of tubulose is prepared, and preparation includes following work
Skill step：
A, cotton is immersed in the cobalt nitrate hexahydrate aqueous solution；
B, it is drawn off being dried after cotton immersion；
C, dried cotton is calcined in air.
Described immersion process is：The cotton of 1-10 parts by weight is immersed to the cobalt nitrate hexahydrate aqueous solution of 90-99 parts by weight
In, cotton will be impregnated with completely.
Described drying means is：The cotton for being adsorbed with cobalt nitrate solution is dried at a temperature of less than 55 DEG C.
Described method for calcinating is：Dried cotton in air in 300-700 DEG C of temperature lower calcination 1-5 hour.
The described cobalt nitrate hexahydrate aqueous solution is：By 1-20 parts by weight cobalt nitrate hexahydrate and 80-99 parts by weight of deionized water
Composition.
The advantages and positive effects of the present invention：
1st, the tubulose cobaltosic oxide for preparing of the present invention compared to the cobaltosic oxide such as spherical have more preferable capacitance characteristic and
Higher energy storage characteristic；
2nd, preparation method of the invention is compared with former preparation method, has simple, low cost, the feature of environmental protection good etc. excellent
Point.
Brief description of the drawings
The present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the X-ray diffractogram of the mesoporous cobaltosic oxide of tubulose prepared using the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of the cobaltosic oxide prepared using the present invention.
Fig. 3 is the nitrogen adsorption-desorption curve and gained tubulose of the mesoporous cobaltosic oxide of tubulose prepared using the present invention
The graph of pore diameter distribution of mesoporous cobaltosic oxide（Insertion portion in figure）.
Fig. 4 is electrode the following in 3.0 M KOH obtained by the mesoporous cobaltosic oxide of tubulose prepared using the present invention
Ring volt-ampere curve.
Fig. 5 is meter of the electrode in 3.0 M KOH obtained by the mesoporous cobaltosic oxide of tubulose prepared using the present invention
When potential curve.
Embodiment
Below by example be further described the present invention, the present embodiment only explanation the present invention concrete mode it
One, the usual variations and alternatives that those skilled in the art are carried out in the range of technical solution of the present invention should all be included in the present invention's
In protection domain.
Embodiment 1：
A kind of preparation of the mesoporous cobaltosic oxide of ultracapacitor tubulose, 1 gram of Co (NO3) 26H2O is first taken to be dissolved in
In 20 grams of deionized waters, then by 1.35 grams of cotton immersion cobalt nitrate aqueous solution.It is drawn off after cotton is impregnated with completely,
53 DEG C of drying in baking oven.Then the cotton for being adsorbed with cobalt nitrate is calcined 3 hours for 400 DEG C in atmosphere.Fig. 1 is final product
XRD, as can be seen from the figure product is Co3O4（Card number is No. 42-1467）.From the ESEM photograph of product（Fig. 2）Can
To learn the pattern of cobaltosic oxide powder as tubulose（8-15 μm of caliber, draw ratio averagely 18, boss ratio 1.1）.Fig. 3 is production
Nitrogen adsorption-desorption curve of thing, understand that product is mesoporous shape porous mass from curve, its aperture is about 9-13nm（In Fig. 3
Insertion figure）.It is 3 m than surface2/g。
The mesoporous cobaltosic oxide powder of the tubulose being prepared is prepared into electrode, then in 3.0 M KOH, voltage belt
Between for 0-0.45 volt carry out cyclic voltammetry curve performance test, as a result as shown in Figure 4, it is possible to find electrode has in KOH solution
Preferable capacitance characteristic.By the electrode being prepared, current density is 0.5 A g in KOH-1Lower test constant current charge and discharge performance point
Analysis, as a result as shown in Figure 5, it is possible to find the specific capacity of electrode of the invention is 130.5 F g-1, electrode of super capacitor can be used as
Materials'use.
Embodiment 2：
A kind of preparation of the mesoporous cobaltosic oxide of ultracapacitor tubulose, 5 grams of Co (NO3) 26H2O are first taken to be dissolved in
In 20 grams of deionized waters, then by 1 gram of cotton immersion cobalt nitrate aqueous solution.It is drawn off, is drying after cotton is impregnated with completely
52 DEG C of drying in case.Then the cotton for being adsorbed with cobalt nitrate is calcined 2 hours for 500 DEG C in atmosphere.Can from the XRD of product
It is Co to go out it3O4（Card number is No. 42-1467）.The shape of cobaltosic oxide powder can be learnt from the ESEM photograph of product
Looks are tubulose（10-20 μm of caliber, draw ratio averagely 20, boss ratio 1.2）.It can sentence from nitrogen adsorption-desorption curve of product
Breaking, it is mesoporous shape porous mass, and its aperture is about 10-18nm.It is 3.7 m than surface2/g。
The mesoporous cobaltosic oxide powder of the tubulose being prepared is prepared into electrode, then in 3.0 M KOH, voltage belt
Between for 0-0.45 volt carry out cyclic voltammetry curve performance test, it is possible to find electrode has preferable capacitance characteristic in KOH solution.
By the electrode being prepared, current density is 0.5 A g in KOH-1Lower test constant current charge and discharge performance evaluation, it is possible to find the present invention
The specific capacity of electrode be 133.7 F g-1, can be used as electrode material for super capacitor.
Embodiment 3：
A kind of preparation of the mesoporous cobaltosic oxide of ultracapacitor tubulose, first take 0.5 gram of Co (NO3) 26H2O dissolving
Immersed in 20 grams of deionized waters, then by 0.5 gram of cotton in the cobalt nitrate aqueous solution prepared.By it after cotton is impregnated with completely
Take out, in an oven 50 DEG C of drying.Then the cotton for being adsorbed with cobalt nitrate is calcined 5 hours for 300 DEG C in atmosphere.From product
XRD can be seen that it is Co3O4（Card number is No. 42-1467）.Cobaltosic oxide can be learnt from the ESEM photograph of product
The pattern of powder is tubulose（7-16 μm of caliber, draw ratio averagely 15, boss ratio 1.1）.It is bent from nitrogen adsorption-desorption of product
Line can determine whether that it is mesoporous shape porous mass, and its aperture is about 2-25nm.It is 3.2 m than surface2/g。
The mesoporous cobaltosic oxide powder of the tubulose being prepared is prepared into electrode, then in 3.0 M KOH, voltage belt
Between for 0-0.45 volt carry out cyclic voltammetry curve performance test, it is possible to find electrode has preferable capacitance characteristic in KOH solution.
By the electrode being prepared, current density is 0.5 A g in KOH-1Lower test constant current charge and discharge performance evaluation, it is possible to find the present invention
The specific capacity of electrode be 128.7 F g-1, can be used as electrode material for super capacitor.
Embodiment 4：
A kind of preparation of the mesoporous cobaltosic oxide of ultracapacitor tubulose, first takes 2 grams of Co (NO3)2·6H2O is dissolved in
In 20 grams of deionized waters, then in cobalt nitrate aqueous solution prepared by 1.3 grams of cotton immersion.Taken after cotton is impregnated with completely
Go out, in an oven 54 DEG C of drying.Then the cotton for being adsorbed with cobalt nitrate is calcined 3.5 hours for 600 DEG C in atmosphere.From product
XRD can be seen that it is Co3O4（Card number is No. 42-1467）.Cobaltosic oxide can be learnt from the ESEM photograph of product
The pattern of powder is tubulose（8-18 μm of caliber, draw ratio averagely 23, boss ratio 1.2）.It is bent from nitrogen adsorption-desorption of product
Line can determine whether that it is mesoporous shape porous mass, and its aperture is about 11-22nm.It is 3.12 m than surface2/g。
The mesoporous cobaltosic oxide powder of the tubulose being prepared is prepared into electrode, then in 3.0 M KOH, voltage belt
Between for 0-0.45 volt carry out cyclic voltammetry curve performance test, it is possible to find electrode has preferable capacitance characteristic in KOH solution.
By the electrode being prepared, current density is 0.5 A g in KOH-1Lower test constant current charge and discharge performance evaluation, it is possible to find the present invention
The specific capacity of electrode be 127.9 F g-1, can be used as electrode material for super capacitor.
Embodiment 5：
A kind of preparation of the mesoporous cobaltosic oxide of ultracapacitor tubulose, first takes 3 grams of Co (NO3)2·6H2O is dissolved in
In 20 grams of deionized waters, then in cobalt nitrate aqueous solution prepared by 1.7 grams of cotton immersion.Taken after cotton is impregnated with completely
Go out, in an oven 51 DEG C of drying.Then the cotton for being adsorbed with cobalt nitrate is calcined 4.5 hours for 700 DEG C in atmosphere.From product
XRD can be seen that it is Co3O4（Card number is No. 42-1467）.Cobaltosic oxide can be learnt from the ESEM photograph of product
The pattern of powder is tubulose（10-18 μm of caliber, draw ratio averagely 23, boss ratio 1.1）.From nitrogen adsorption-desorption of product
Curve can determine whether that it is mesoporous shape porous mass, and its aperture is about 6-19 nm.It is 3.3 m than surface2/g。
The mesoporous cobaltosic oxide powder of the tubulose being prepared is prepared into electrode, then in 3.0 M KOH, voltage belt
Between for 0-0.45 volt carry out cyclic voltammetry curve performance test, it is possible to find electrode has preferable capacitance characteristic in KOH solution.
By the electrode being prepared, current density is 0.5 A g in KOH-1Lower test constant current charge and discharge performance evaluation, it is possible to find the present invention
The specific capacity of electrode be 133.1 F g-1, can be used as electrode material for super capacitor.
Claims (3)
- A kind of 1. preparation method of the mesoporous cobaltosic oxide of ultracapacitor tubulose, it is characterised in that：Using cotton as template, with Cobalt nitrate hexahydrate is raw material, soaking, dry and calcination process, the mesoporous cobaltosic oxide product of tubulose is prepared, prepares bag Include following processing step：A, cotton is immersed in the cobalt nitrate hexahydrate aqueous solution；B, it is drawn off being dried after cotton immersion；C, dried cotton is calcined in air to obtain product；Described immersion process is：The cotton of 1-10 parts by weight is immersed in the cobalt nitrate hexahydrate aqueous solution of 90-99 parts by weight, cotton Flower will be impregnated with completely；Described drying means is：The cotton for being adsorbed with cobalt nitrate solution is dried at a temperature of less than 55 DEG C；Described method for calcinating is：Dried cotton in air in 300-700 DEG C of temperature lower calcination 1-5 hour；The described cobalt nitrate hexahydrate aqueous solution is：It is made up of 1-20 parts by weight cobalt nitrate hexahydrate and 80-99 parts by weight of deionized water.
- 2. the preparation method of the mesoporous cobaltosic oxide of ultracapacitor tubulose according to claim 1, it is characterised in that first Take 5 grams of Co (NO3) 26H2O to be dissolved in 20 grams of deionized waters, then 1 gram of cotton is immersed in cobalt nitrate aqueous solution；Treat cotton Use up and be drawn off after being impregnated with entirely, in an oven 52 DEG C of drying；Then the cotton for being adsorbed with cobalt nitrate is forged for 500 DEG C in atmosphere Burn 2 hours and obtain product.
- 3. a kind of preparation method as claimed in claim 1 or 2 obtains the mesoporous cobaltosic oxide product of tubulose, its characteristic is：Aperture Be 8-20 μm for 9-25nm, caliber, boss ratio be more than 1, draw ratio be more than be 10.
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Citations (3)
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| CN101863518A (en) * | 2010-07-01 | 2010-10-20 | 上海应用技术学院 | Co3O4 nano hollow sphere material and preparation method and application thereof |
| CN103265007A (en) * | 2013-05-14 | 2013-08-28 | 上海理工大学 | Preparation method of ordered mesoporous carbon material containing magnetic metal particles |
| CN103450475A (en) * | 2013-09-13 | 2013-12-18 | 中北大学 | Method for preparing core-shell structured conductive polyaniline/Co3O4 powder |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863518A (en) * | 2010-07-01 | 2010-10-20 | 上海应用技术学院 | Co3O4 nano hollow sphere material and preparation method and application thereof |
| CN103265007A (en) * | 2013-05-14 | 2013-08-28 | 上海理工大学 | Preparation method of ordered mesoporous carbon material containing magnetic metal particles |
| CN103450475A (en) * | 2013-09-13 | 2013-12-18 | 中北大学 | Method for preparing core-shell structured conductive polyaniline/Co3O4 powder |
Non-Patent Citations (1)
| Title |
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| "钴化合物超级电容器复合电极材料的制备及其性能研究";刘萍;《中国优秀硕士学位论文全文数据库 工程科II辑》;20130515;第24-48页 * |
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