CN108172410B - Spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite and its preparation method and application - Google Patents
Spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite and its preparation method and application Download PDFInfo
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 58
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 title claims abstract description 57
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000000047 product Substances 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007772 electrode material Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 7
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 235000013495 cobalt Nutrition 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012257 stirred material Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Chemical compound [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 10
- 238000005119 centrifugation Methods 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 9
- 230000004087 circulation Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- -1 cadmium oxide compound Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HUKFCVYEXPZJJZ-UHFFFAOYSA-N cadmium;hydrate Chemical compound O.[Cd] HUKFCVYEXPZJJZ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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, 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
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a kind of spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposites and its preparation method and application, then reaction product should be calcined so that spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite is made the preparation method comprises the following steps: cobalt source, cadmium source, ammonium hydrogen carbonate are carried out hydro-thermal reaction in organic solvent.The spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite has preferable capacitance and cyclical stability, so that its electrode material that can be competent at supercapacitor or lithium ion battery, while the preparation method has the advantages that easy low in cost, mild condition, environmentally protective, easy to operate, product post-processing, Product size and morphology controllable.
Description
Technical field
The present invention relates to nanocomposites, and in particular, to a kind of nano combined material of spherical cobaltic-cobaltous oxide/cadmium oxide
Material and its preparation method and application.
Background technique
Supercapacitor, also referred to as electrochemical capacitor, due to its high power density, fast ion exchange rate and long circulating
Service life, therefore it plays an important role in supplement lithium ion battery energy storage cause.
In recent years, in order to find novel, low-cost electrode material, researchers to transition metal material in, by
Have widely in its property with unique physics and chemistry, thus in fields such as catalysis, electrochemistry and gas sensors
Using so as to cause the high interest of people.
The performance of electrochemical capacitor is largely dependent on its electrode material, and composition and structure with electrode material
There is vital connection.The shape characteristic and microstructure of cobaltosic oxide have important shadow to its performance and application
It rings.The pattern of cobaltosic oxide is largely studied, and has successfully synthesized nanometer sheet at present, nano wire, nanometer rods and is received
The structures such as rice ball.Currently, synthesis nano-cobaltic-cobaltous oxide method multiplicity, can use hydro-thermal, solvent thermal reaction, pass through electrochemical deposition
Legal system must wait.But the preparation method of current nano-cobaltic-cobaltous oxide have the defects that it is at high cost or not environmentally and nanometer
That there are chemical properties in performance is relatively small for cobaltosic oxide, and the unstable defect of long-term cycle performance.
Summary of the invention
The object of the present invention is to provide a kind of spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite and preparation method thereof and
Using, the spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite has preferable capacitance and cyclical stability, so that
Its electrode material that can be competent at supercapacitor or lithium ion battery, while the preparation method has low in cost, condition temperature
The advantages of with environmentally protective, easy to operate, product post-processing simplicity, Product size and morphology controllable.
To achieve the goals above, the present invention provides a kind of spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposites
Preparation method, should be the preparation method comprises the following steps: carry out hydro-thermal reaction for cobalt source, cadmium source, ammonium hydrogen carbonate, then by reaction in organic solvent
Product is calcined so that spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite is made.
The present invention also provides a kind of spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite, the spherical cobaltic-cobaltous oxide/
Cadmium oxide nanocomposite is prepared by above-mentioned preparation method.
The present invention also provides a kind of if above-mentioned spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite is asymmetric counterfeit
Application in capacitor electrode material.
In the above-mentioned technical solutions, the present invention passes through chemical liquid deposition organic by cobalt source, cadmium source, ammonium hydrogen carbonate
Haptoreaction is carried out in solvent, Co is made3O4/ CdO nanocomposite, the composite material is in 2Ag-1Current density under
Quality capacitor can reach 453.6Fg-1；After 7000 circulations, capacitor is still able to maintain the 94.1% of initial value, illustrates spherical shape
Co3O4/ CdO nanocomposite has good cyclical stability.The above method uses one step hydro thermal method, has simple easy
Operation, low in cost, mild condition, the advantages that environmentally protective, the time is short, product easily obtains；During the reaction without being added
Any stabilizer, template or surfactant, the convenient post-treatment of product are easy to adjust the size and shape of material
Control is suitble to large-scale production.Wherein most importantly spherical cobaltic-cobaltous oxide electrode material by cadmium oxide compound so that
Nanostructure is opposite to be reduced, so that chemical property improves a lot.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 a is Co prepared by embodiment 13O4The scanning electron microscope of 60K times of the amplification of/CdO nanocomposite
(SEM) figure；
Fig. 1 b is Co prepared by embodiment 13O4The scanning electron microscope of 12K times of the amplification of/CdO nanocomposite
(SEM) figure；
Fig. 2 is Co prepared by embodiment 13O4Transmission electron microscope (TEM) figure of/CdO nanocomposite；
Fig. 3 is Co prepared by embodiment 13O4X-ray diffraction pattern (XRD) figure of/CdO nanocomposite；
Fig. 4 is Co prepared by embodiment 13O4/ CdO nanocomposite exchanges resistance with after 7000 circle circulations before circulation
Anti- curve graph；
Fig. 5 is Co prepared by embodiment 13O4The cyclic voltammetry curve figure of/CdO nanocomposite；
Fig. 6 is Co prepared by embodiment 13O4Constant current charge-discharge of/CdO the nanocomposite under different current densities is bent
Line chart；
Fig. 7 is Co prepared by embodiment 13O4/ CdO nanocomposite sweeps fast Shi Xunhuan-specific capacitance curve in 60mV/s
Figure.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite preparation method, the preparation sides
Method are as follows: cobalt source, cadmium source, ammonium hydrogen carbonate are subjected to hydro-thermal reaction in organic solvent, then calcine reaction product to make
Obtain spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite.
In the above preparation method, the specific dosage of each material can select in a wide range, but in order to make to be made
Product have higher yield and superior chemical property, it is preferable that cobalt source, cadmium source, ammonium hydrogen carbonate, organic solvent
Amount ratio be 0.5-2.0mmol:0.2-1.0mmol:10-15mmol:20-40ml.
In the above preparation method, the condition of hydro-thermal reaction can select in a wide range, but obtained in order to make
Product has higher yield and superior chemical property, it is preferable that hydro-thermal reaction meets the following conditions: reaction temperature
It is 170-200 DEG C, reaction time 8-14h.
In the above preparation method, calcination condition can select in a wide range, but in order to make product tool obtained
Have superior chemical property, it is preferable that calcining meets the following conditions: calcination temperature is 400-500 DEG C, and calcination time is
0.5-2h。
In the above preparation method, the specific type of each material can select in a wide range, but from environmental protection and
Economic angle considers, it is preferable that cobalt source is selected from least one of four acetate hydrate cobalt cobalt chlorides and cabaltous nitrate hexahydrate, cadmium source
At least one of four nitric hydrate cadmium caddies and cadmium sulfate, organic solvent are selected from ethylene glycol.
In the above preparation method, in order to which hydro-thermal reaction can be sufficiently carried out, it is preferable that, should before hydro-thermal reaction
It is 8-15min that preparation method, which further includes the time for being stirred material, and stirring,.
In the above preparation method, in order to which the purity of the product of hydro-thermal reaction is further enhanced while imitates calcining
Fruit is more excellent, it is preferable that after hydro-thermal reaction, which further includes being cooled to the mixture after reaction
It 20-25 DEG C, is then centrifuged for collecting product, wash products, drying；Wherein, cleaning passes sequentially through deionized water and ethyl alcohol respectively cleans
2-4 mode carries out, and drying handles 8-14h at 55-65 DEG C.
The present invention also provides a kind of spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite, the spherical cobaltic-cobaltous oxide/
Cadmium oxide nanocomposite is prepared by above-mentioned preparation method.
In above-mentioned spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite, the average grain diameter of nanocomposite can be with
It selects in a wide range, but in order to further increase the chemical property of nanocomposite, it is preferable that spherical shape four aoxidizes
Three cobalts/cadmium oxide nanocomposite average grain diameter is 170-210nm, preferably 180-200nm.
The present invention also provides a kind of if above-mentioned spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite is asymmetric counterfeit
Application in capacitor electrode material.
The present invention will be described in detail by way of examples below.
Embodiment 1
By 0.8mmol Co (CH3COO)2·4H2O、0.3mmol Cd(NO3)2·4H2O and 13mmol NH4HCO3It is dissolved in
In 25mL ethylene glycol, 8min is stirred, solution is obtained, transfers the solution into 50mL reaction kettle and seal, the hydro-thermal reaction at 170 DEG C
8h is cooled to 25 DEG C, product is collected by centrifugation, and is respectively washed centrifugation 2 times with deionized water and ethyl alcohol, then dry at 60 DEG C
The sample of drying is finally put into 420 DEG C of calcining 1h in Muffle furnace, obtains spherical Co by 8h3O4/ CdO nanocomposite.
Embodiment 2
By 1mmol Co (CH3COO)2·4H2O、0.5mmol Cd(NO3)2·4H2O and 15mmol NH4HCO3It is dissolved in
In 30mL ethylene glycol, 10min is stirred, solution is obtained, transfers the solution into 50mL reaction kettle and seal, hydro-thermal is anti-at 190 DEG C
12h is answered, 25 DEG C is cooled to, product is collected by centrifugation, centrifugation 3 times is respectively washed with deionized water and ethyl alcohol, is then done at 60 DEG C
The sample of drying is finally put into 450 DEG C of calcining 1h in Muffle furnace, obtains spherical Co by dry 12h3O4/ CdO nanocomposite.
Embodiment 3
By 1.2mmol Co (CH3COO)2·4H2O、0.7mmol Cd(NO3)2·4H2O and 17mmol NH4HCO3It is dissolved in
In 35mL ethylene glycol, 12min is stirred, solution is obtained, transfers the solution into 50mL reaction kettle and seal, hydro-thermal is anti-at 200 DEG C
13h is answered, 25 DEG C is cooled to, product is collected by centrifugation, centrifugation 4 times is respectively washed with deionized water and ethyl alcohol, is then done at 60 DEG C
The sample of drying is finally put into 470 DEG C of calcining 1.5h in Muffle furnace, obtains spherical Co by dry 14h3O4/ CdO nanocomposite.
Embodiment 4
By 0.9mmol Co (CH3COO)2·4H2O、0.4mmol Cd(NO3)2·4H2O and 14mmol NH4HCO3It is dissolved in
In 28mL ethylene glycol, 10min is stirred, solution is obtained, transfers the solution into 50mL reaction kettle and seal, hydro-thermal is anti-at 180 DEG C
10h is answered, 25 DEG C is cooled to, product is collected by centrifugation, centrifugation 3 times is respectively washed with deionized water and ethyl alcohol, is then done at 60 DEG C
The sample of drying is finally put into 430 DEG C of calcining 1.2h in Muffle furnace, obtains spherical Co by dry 9h3O4/ CdO nanocomposite.
Embodiment 5
By 1.1mmol Co (CH3COO)2·4H2O、0.6mmol Cd(NO3)2·4H2O and 16mmol NH4HCO3It is dissolved in
In 32mL ethylene glycol, 11min is stirred, solution is obtained, transfers the solution into 50mL reaction kettle and seal, hydro-thermal is anti-at 190 DEG C
10h is answered, 25 DEG C is cooled to, product is collected by centrifugation, centrifugation 4 times is respectively washed with deionized water and ethyl alcohol, is then done at 60 DEG C
The sample of drying is finally put into 460 DEG C of calcining 1h in Muffle furnace, obtains spherical Co by dry 13h3O4/ CdO nanocomposite.
Detect example 1
(1) morphology analysis is carried out to 1 products therefrom of embodiment with scanning electron microscope (SEM), as a result such as Fig. 1 a and figure
Shown in 1b, show that prepared sample is spherical nanostructure.
(2) 1 products therefrom ingredient of embodiment is analyzed with transmission electron microscope (TEM), as a result such as Fig. 2 institute
Show, can significantly find out that sample is porous spherical structure.By Fig. 1 a, Fig. 1 b and Fig. 2 it is found that the average grain of spherical nanostructure
Diameter is 170-210nm.
(3) 1 products therefrom of embodiment is detected with X-ray diffraction (XRD), as a result as shown in figure 3, obtaining map and JCPDS
Co corresponding to standard card NO.76-18023O4It fits like a glove with CdO diffraction maximum corresponding to NO.65-2908.This XRD diagram can
To prove the substance for Co well3O4/ CdO nanocomposite.
Product is made to embodiment 2-5 in the same manner to detect, the product of testing result and embodiment 1
Testing result is almost the same.
Application examples 1
It tests and is carried out in CHI660E electrochemical workstation (manufacture of Shanghai Chen Hua Instrument Ltd.) below.Below
Test is all made of three-electrode system, wherein the Co for preparing embodiment 13O4/ CdO nanocomposite is as working electrode；Platinum
Silk electrode and saturated calomel electrode (SCE) are respectively as to electrode and reference electrode；Electricity is carried out in 3mol/L KOH electrolyte
Chemical property test.
(1) electrochemical impedance spectroscopy is tested
Co is obtained by electrochemical impedance spectroscopy3O4/ CdO nanocomposite electrode exchanges resistance before and after the circle of circulation 7000
Anti- map comparison, as shown in figure 4, black curve indicates Co3O4The AC impedance of/CdO nanocomposite electrode before the loop
Curve, red curve indicate Co3O4The AC impedance curve of/CdO nanocomposite electrode after 7000 circle circulations.
Ac impedance spectroscopy is divided into high frequency region part and low frequency range part, by the arc and low frequency range of one section of semicircle of high frequency region
A skew lines composition.It is Co in the intersection point of high frequency region impedance spectrum and real axis3O4The internal resistance of/CdO nanocomposite electrode,
The resistance of resistance, electrolyte including active material itself and the contact resistance of active material and electrolyte.Low frequency range can be with
It was found that Co3O4/ CdO nanocomposite electrode before the loop with after 7000 circulations when the slope of curve it is approximate, before circulation
It is very nearly the same with the diffusional resistance after circulation, it has been indicated above Co3O4/ CdO nanocomposite electrode can be used as super capacitor
The electrode material of device.
(2) cyclic voltammetry (CV) is tested
Respectively with 5mVs-1、20mV·s-1、40mV·s-1、60mV·s-1、80mV·s-1And 100mVs-1Scanning
Rate is scanned, and obtains Co in embodiment 13O4The cyclic voltammetry curve of/CdO nanocomposite is as shown in figure 5, the curve
Potential range be 0-0.6V.
(3) constant current charge-discharge (CP) is tested
Respectively in 2Ag-1、4A·g-1、6A·g-1And 8Ag-1、10A·g-1Lower progress constant current charge-discharge detection, obtains
Co in embodiment 13O4The constant current charge-discharge curve of/CdO nanocomposite under different current densities, as shown in Figure 6.Its
In, ordinate, that is, voltage range of the curve is 0-0.5V.The specific capacitance under different current densities is calculated by following equation
Charge and discharge.Go out specific capacitance, i.e. Co by charge and discharge graphic calculation3O4/ CdO nanocomposite is in 2Ag-1Specific capacitance under current density
For 453.6Fg-1, illustrate Co3O4/ CdO nanocomposite has the performance of good storage electricity.
Wherein, capacitor calculation formula are as follows: Cm=(It)/(△ Vm), I are size of current, and t is discharge time, and △ V is
Potential difference, m are the quality of working electrode piece load.
(4) cycle performance detects
In 60mVs-1It sweeps and is recycled 7000 times under speed, obtain the Co in embodiment 13O4/ CdO nanocomposite follows
Ring-specific capacitance curve, as a result as shown in fig. 7, by termination capacity and initial capacity comparison it is found that after 7000 circulations and just
Beginning capacitor is close, illustrates Co3O4/ CdO nanocomposite has excellent stability.
Product is made to embodiment 2-5 in the same manner to detect, the product of testing result and embodiment 1
Testing result is almost the same.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (8)
1. a kind of spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite preparation method, which is characterized in that the preparation method
Are as follows: cobalt source, cadmium source, ammonium hydrogen carbonate are subjected to hydro-thermal reaction in organic solvent, then calcine reaction product to be made
The spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite；
Wherein, the hydro-thermal reaction meets the following conditions: reaction temperature is 170-200 DEG C, reaction time 8-14h；It is described to forge
Burning meets the following conditions: calcination temperature is 400-500 DEG C, calcination time 0.5-2h；The cadmium source be selected from four nitric hydrate cadmiums,
At least one of caddy and cadmium sulfate.
2. preparation method according to claim 1, wherein the cobalt source, cadmium source, ammonium hydrogen carbonate, organic solvent dosage
Than for 0.5-2.0mmol:0.2-1.0mmol:10-15mmol:20-40ml.
3. preparation method according to claim 1, wherein the cobalt source is selected from four acetate hydrate cobalts, cobalt chloride and six water
At least one of cobalt nitrate is closed, the organic solvent is selected from ethylene glycol.
4. preparation method described in any one of -3 according to claim 1, wherein before the hydro-thermal reaction, the system
Preparation Method further includes being stirred material, and the time of the stirring is 8-15min.
5. preparation method described in any one of -3 according to claim 1, wherein after the hydro-thermal reaction, the system
Preparation Method further includes carrying out the mixture after reaction to be cooled to 20-25 DEG C, is then centrifuged for collecting product, wash products, drying；
Wherein, the cleaning, which passes sequentially through deionized water and ethyl alcohol and respectively cleans 2-4 mode, carries out, and the drying is in 55-65
8-14h is handled at DEG C.
6. a kind of spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite, which is characterized in that the spherical cobaltic-cobaltous oxide/oxygen
Cadmium nanocomposite is prepared by preparation method described in any one of claim 1-5.
7. spherical cobaltic-cobaltous oxide according to claim 6/cadmium oxide nanocomposite, wherein spherical four oxygen
Changing three cobalts/cadmium oxide nanocomposite average grain diameter is 170-210nm.
8. a kind of spherical cobaltic-cobaltous oxide/cadmium oxide nanocomposite as claimed in claims 6 or 7 is in asymmetric fake capacitance
Application in device electrode material.
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| CN102795603A (en) * | 2011-05-26 | 2012-11-28 | 中国科学院大连化学物理研究所 | Preparation method for simultaneously obtaining porous metal oxide nano material and high-purity perylene |
| CN106449172A (en) * | 2016-10-19 | 2017-02-22 | 安徽师范大学 | CdS @ Ni3S2 core-shell heterostructure composite material, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102795603A (en) * | 2011-05-26 | 2012-11-28 | 中国科学院大连化学物理研究所 | Preparation method for simultaneously obtaining porous metal oxide nano material and high-purity perylene |
| CN106449172A (en) * | 2016-10-19 | 2017-02-22 | 安徽师范大学 | CdS @ Ni3S2 core-shell heterostructure composite material, preparation method and application thereof |
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| Title |
|---|
| "Preparation and characterization of uniform coated particles(Cobalt compounds on cadmium compounds)";I.U.HAQ等;《Journal of materials science》;20001231;第35卷;实验部分-结果分析 * |
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