CN106356198B - A kind of mesoporous ZnCo2O4Nanometer sheet@NiCo2O4Nanowire composite, preparation method and applications - Google Patents
A kind of mesoporous ZnCo2O4Nanometer sheet@NiCo2O4Nanowire composite, preparation method and applications Download PDFInfo
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- CN106356198B CN106356198B CN201610844077.6A CN201610844077A CN106356198B CN 106356198 B CN106356198 B CN 106356198B CN 201610844077 A CN201610844077 A CN 201610844077A CN 106356198 B CN106356198 B CN 106356198B
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910005949 NiCo2O4 Inorganic materials 0.000 claims abstract description 40
- 239000002070 nanowire Substances 0.000 claims abstract description 36
- 229910003119 ZnCo2O4 Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007772 electrode material Substances 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 59
- 239000006260 foam Substances 0.000 claims description 26
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 15
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 239000011686 zinc sulphate Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006276 transfer reaction Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 229910003266 NiCo Inorganic materials 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- -1 Polytetrafluoroethylene Polymers 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 230000003466 anti-cipated effect Effects 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical class [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000035040 seed growth Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The present invention provides a kind of mesoporous ZnCo2O4Nanometer sheet@NiCo2O4Nanowire composite, preparation method and its use.Compared with prior art, the present invention is by simple cryochemistry liquid phase method, in mesoporous ZnCo2O4Composite mesopore NiCo in nanometer chip architecture2O4Nano wire obtains mesoporous ZnCo2O4Nanometer sheet@NiCo2O4Nanowire composite structures.The application of Asymmetric Supercapacitor electrode material provided by the present invention has the advantages that big specific capacity, good cycling stability, power density and energy density is high and preparation process is simple, of low cost.
Description
Technical field
The invention belongs to preparation method of nano material and electrochemistry cross-application fields, and in particular to a kind of mesoporous ZnCo2O4
Nanometer sheet@NiCo2O4Nanowire composite, preparation method and applications.
Background technology
Demand of the today's society to the advanced energy-storage system of high power device (such as electric vehicle and mobile electronic device) is held
It is continuous to increase.Since power density is high, charge and discharge process is fast and has extended cycle life etc., unique advantage has attracted generation to ultracapacitor
Researcher more and more pays close attention within the scope of boundary.
Electrode material is to determine the vital factor of ultracapacitor chemical property, the electrode material of synthesized high-performance
The practical application for improving ultracapacitor is practical.Spinel structure transition metal ternary oxide, such as ZnCo2O4、
NiCo2O4Deng have the electric conductivity more much higher than corresponding one-component oxide, be capable of providing more rich redox reaction,
To have better specific capacitance and cycle life in supercapacitor applications.But the conduction of these materials still relative mistake
Property hinders their further practical applications.
Invention content
The object of the present invention is to provide a kind of mesoporous ZnCo2O4Nanometer sheet@NiCo2O4Nanowire composite and its system
Preparation Method, using cryochemistry liquid phase method, using nickel foam as the synthesising mesoporous ZnCo of conductive substrates2O4Nanometer sheet@NiCo2O4Nanometer
Line is classified composite nanostructure material, simple for process, at low cost.
The present invention also provides a kind of mesoporous ZnCo2O4Nanometer sheet@NiCo2O4Nanowire composite is as asymmetric super
The application of grade capacitor electrode material.
A kind of mesoporous ZnCo provided by the invention2O4Nanometer sheet@NiCo2O4The preparation method of nanowire composite, including
Following steps：
(1) by ZnSO4·7H2O、CoSO4·7H2O, tetrabutylammonium bromide and NaHCO3Dissolving in deionized water, is stirred
Mixing obtains solution A, solution A is transferred in reaction kettle, nickel foam is tiltedly placed in solution, sealing, heating reaction, natural
It is cooled to room temperature, washs, dries, obtain the nickel foam of presoma；
(2) by Ni (NO3)2·6H2O、Co(NO3)2·6H2O, tetrabutylammonium bromide and NaHCO3It is dissolved in deionized water
In, it stirs and evenly mixs, obtains solution B, by solution B transfer reaction kettle, nickel foam prepared by step (1) is tiltedly placed in solution,
Sealing, heating reaction, cooled to room temperature is washed, dry, and calcining obtains mesoporous ZnCo2O4Nanometer sheet@NiCo2O4Nanometer
Line composite material.
Further, ZnSO in step (1)4·7H2O、CoSO4·7H2O, tetrabutylammonium bromide and NaHCO3Molar ratio
It is 1:2:1:2, a concentration of 0.025M of the tetrabutylammonium bromide in solution A.
The use of nickel foam described in step (1) is preceding through over cleaning, specially：6M dilute hydrochloric acid is first used to impregnate 10min removings outer
The oxidation film of layer, is then cleaned with deionized water.Nickel foam after cleaning is cut to 2 × 3cm sizes.
Step stirs described in (1), time 20-30min；
Reaction is heated described in step (1), specially：6-12h is reacted at 180 DEG C.
Ni (NO in step (2)3)2·6H2O、Co(NO3)2·6H2O, tetrabutylammonium bromide and NaHCO3Molar ratio be
1:2:1:2；Tetrabutylammonium bromide a concentration of 0.025M in solution B.
Step stirs described in (2), time 20-30min；
Reaction is heated described in step (2), specially：6-12h is reacted at 180 DEG C of temperature.
Step is calcined described in (2), specially：5 DEG C of min of heating rate-1, 2-3h is calcined at 400 DEG C of temperature.
A kind of mesoporous ZnCo provided by the invention2O4Nanometer sheet@NiCo2O4Nanowire composite, using above method system
It is standby to obtain.Product is the mesoporous ZnCo of 2 μm of average transverse2O4The mesoporous NiCo of the compound average diameter 5nm of nanometer sheet2O4It receives
Rice noodles.
The present invention provides a kind of mesoporous ZnCo2O4Nanometer sheet@NiCo2O4Nanowire composite is as asymmetric super
The application of capacitor electrode material.
Concrete application method is：
With the mesoporous ZnCo of preparation2O4Nanometer sheet@NiCo2O4Nanowire composite is anode, activated carbon electrodes (AC) are
Cathode is assembled into Asymmetric Supercapacitor device, and electrolyte is 3M KOH solutions.It is surveyed using CHI 660D electrochemical workstations
Measure cyclic voltammetry curve, constant current charge-discharge and charge and discharge cycles.The test of cyclic voltammetry curve is in 10,25,50 Hes
100mV s-1It is carried out under different scanning speed, voltage range is 0~1.5V.Constant current charge-discharge is tested in 1,2,5,10 and 20A
g-1It is carried out under different current densities, 0~1.45V of voltage range.
The present invention is using nickel foam as conductive substrates, by simple cryochemistry liquid phase method, in NaHCO3What hydrolysis provided
Under alkaline condition, Zn2+、Co2+Hydrolysis, obtains ZnCo2O4Predecessor seed, under the orientation absorption of tetrabutylammonium cation,
ZnCo2O4Predecessor orientation connects into a nanometer chip architecture.Further in NaHCO3It hydrolyzes under the alkaline condition provided, Ni2+And Co2 +Ion hydrolyzes, in ZnCo2O4NiCo is grown in predecessor nanometer sheet2O4Predecessor seed.In the orientation of tetrabutylammonium cation
Under absorption, NiCo2O4Predecessor seed growth obtains ZnCo2O4Nanometer sheet@NiCo2O4Nano wire predecessor.Finally calcining release
After small molecule, mesoporous ZnCo is obtained2O4Nanometer sheet@NiCo2O4Nano wire is classified composite nanostructure material.It is classified composite Nano
Structure can shorten the diffusion length of electrolyte ion, develop more effective electron-transport path, and then improve the conduction of material
Property and stability.Moreover, classification nanostructure can prevent material from reuniting, it is convenient for fast ionic and electronics transfer, ensures all
Component participate in electrochemical process completely, to promote electrochemical properties.The present invention utilizes difference in classification composite nanostructure
Synergistic effect between component promotes the fortune of ion and electronics during faraday's redox reaction between electrode and electrolyte
It is defeated, and NiCo2O4ZnCo can be protected in branched structure oxidation-reduction process2O4Skeleton structure it is complete, improve the conduction of material
Property, stability, and then improve the performances such as specific capacitance, cyclical stability, power density and energy density.
Compared with prior art, the present invention is in mesoporous ZnCo2O4Composite mesopore NiCo in nanometer chip architecture2O4Nano wire,
Obtain mesoporous ZnCo2O4Nanometer sheet@NiCo2O4Nanowire composite structures.Asymmetric Supercapacitor electrode provided by the present invention
The application of material, have specific capacitance big, good cycling stability, power density and energy density is high and preparation process is simple, at
This cheap advantage.
Description of the drawings
Fig. 1 is mesoporous ZnCo prepared by embodiment 12O4Nanometer sheet@NiCo2O4The x-ray powder of nanowire composite spreads out
Penetrate (XRD) figure；
Fig. 2 is mesoporous ZnCo prepared by embodiment 12O4Nanometer sheet@NiCo2O4The Flied emission of nanowire composite scans
Electron microscope (FESEM) figure；
Fig. 3 is mesoporous ZnCo prepared by embodiment 12O4Nanometer sheet@NiCo2O4The transmitted electron of nanowire composite is aobvious
Micro mirror (TEM) figure；
Fig. 4 is mesoporous ZnCo prepared by embodiment 12O4Nanometer sheet@NiCo2O4The high-resolution lattice of nanowire composite
Striped (HRTEM) image；
Fig. 5 is 2 mesoporous ZnCo of embodiment2O4Nanometer sheet@NiCo2O4Nanowire composite asymmetric electrode system testing
Cyclic voltammetry curve；Sweep speed is 100 mV s according to this from top to bottom-1, 50mV s-1, 25mV s-1, 10mV s-1；
Fig. 6 is 2 mesoporous ZnCo of embodiment2O4Nanometer sheet@NiCo2O4Nanowire composite asymmetric electrode system testing
Constant current charge-discharge curve；Current density is 2.5A g according to this from right to left-1, 5A g-1, 10A g-1With 20A g-1；
Fig. 7 is 2 mesoporous ZnCo of embodiment2O4Nanometer sheet@NiCo2O4Nanowire composite asymmetric electrode system testing
Specific capacitance cycle figure；
Fig. 8 is 2 mesoporous ZnCo of embodiment2O4Nanometer sheet@NiCo2O4The Asymmetric Electric electrode systems of nanowire composite are surveyed
The energy density of examination and saturation effect curve (Ragone curves).
Specific implementation mode
Embodiment 1
A kind of mesoporous ZnCo2O4Nanometer sheet@NiCo2O4The preparation method of nanowire composite, includes the following steps：
(1) by 1mmol ZnSO4·7H2O, 2mmol CoSO4·7H2O and 1mmol tetrabutylammonium bromide is dissolved in successively
In 40mL deionized waters, 2mmol NaHCO are then added3, 20min is persistently stirred, solution A is obtained.Solution A is transferred to 50mL
Polytetrafluoroethylene (PTFE) be liner reaction kettle in, the nickel foam of the 2 × 3cm anticipated (is first used into the immersion of 6M dilute hydrochloric acid
10min removes the oxidation film of outer layer, is then cleaned with deionized water) tiltedly it is placed in solution, it seals and heats 12h at 180 DEG C,
Cooled to room temperature.The nickel foam deionized water and absolute ethyl alcohol for covering sample are respectively washed 3 times, and 60 DEG C of vacuum drying chambers are placed in
Middle dry 6h.
(2) by 0.1mmol Ni (NO3)2·6H2O, 0.2mmol Co (NO3)2·6H2O and 0.1mmol tetrabutyl phosphonium bromides
Ammonium is dissolved in successively in 40mL deionized waters, and 0.2mmol NaHCO are then added3, 20min is persistently stirred, solution B is obtained.It will
Solution B is transferred in the reaction kettle that 50mL polytetrafluoroethylene (PTFE) is liner, and the nickel foam of above-mentioned covering sample is tiltedly placed on solution
In, it seals and heats 12h, cooled to room temperature at 180 DEG C.Cover the nickel foam deionized water and absolute ethyl alcohol of sample
It respectively washes 3 times, is placed in 60 DEG C of vacuum drying chambers dry 6h.Later, the nickel foam for covering sample is placed in muffle furnace with 5 DEG C
min-1Rate be warming up to 400 DEG C calcining 2h.
The structure and morphology characterization of sample：
Using XRD-6000 type x-ray powder diffraction instruments characterize sample object phase (ultrasound collect powder sample test, avoid
Base foam nickel interferes), as shown in Figure 1.All diffraction maximums can be using index as Spinel ZnCo2O4(JCPDS card numbers：
23-1390) and NiCo2O4(JCPDS card numbers：73-1702).Show sample by Spinel ZnCo2O4And NiCo2O4It constitutes.
The morphology and size of sample is observed using Hitachi's S-4800 field emission scanning electron microscopes (FESEM), as shown in Figure 2.Show
Sample is the nano thread structure of the compound average diameter 5nm of nanometer sheet of 2 μm of average transverse.Electricity is transmitted using JEOL 2010
Sub- microscope further looks at the pattern of sample, and the results are shown in Figure 3.Show that sample is meso-porous nano piece composite mesopore nano wire
Structure.Further the shell of sample is analyzed using high resolution transmission electron microscopy, the results are shown in Figure 4.Interplanar
Shell NiCo is corresponded to respectively away from 0.47nm and 0.29nm2O4(111) and (220) crystal face of nano wire.
Embodiment 2
A kind of mesoporous ZnCo2O4Nanometer sheet@NiCo2O4The Asymmetric Supercapacitor electrode material of nanowire composite
Application.
Concrete application method is：
With mesoporous ZnCo2O4Nanometer sheet@NiCo2O4Nanowire composite is anode and activated carbon electrodes (AC) are cathode
It is assembled into Asymmetric Supercapacitor device, using 3M KOH solutions as electrolyte, is measured using CHI 660D electrochemical workstations
Cyclic voltammetry curve, constant current charge-discharge and charge and discharge cycles.The test of cyclic voltammetry curve is in 10,25,50 and 100mV
s-1It is carried out under different scanning speed, voltage range is 0~1.5V, and the results are shown in Figure 5.100mV s are arrived 10-1Sweep fast range
Interior CV curves do not distort significantly, show Asymmetric Supercapacitor fast charging and discharging feature.And it can be clear from CV curves
Find out that the total capacitance of asymmetric capacitor derives from the comprehensive contribution of Faraday pseudo-capacitance and electric double layer capacitance clearly.Constant current fills
Discharge test is in 1,2,5,10 and 20A g-1It is carried out under different current densities, voltage range is 0~1.45V, as a result such as Fig. 6 institutes
Show.It is 1,2,5,10 and 20A g to be calculated in current density-1When specific capacitance be respectively 604.9,522.3,452.7,
384.0 with 290.7F g-1.The stability of charge and discharge cycles, with current density for 5A g-1For, it is (same that the results are shown in Figure 7
When provide ZnCo2O4The result of nanometer sheet is to make comparisons).Show sample after cycle 5000 times, mesoporous ZnCo2O4Nanometer sheet@
NiCo2O4The specific capacitance of nanowire composite electrode can keep 98.8% initial (ZnCo2O4Nanometer sheet 5A g-1When head
Secondary specific capacitance is 219.7F g-1, specific capacitance residue 94.2% after recycling 5000 times).Mesoporous ZnCo2O4Nanometer sheet@NiCo2O4It receives
Rice noodles composite material illustrates the cyclical stability that high specific capacitance is become reconciled.The Asymmetric Supercapacitor of composite material assembling
The functional relation of power density and energy density, as shown in Figure 8 (while providing ZnCo2O4The result of nanometer sheet is to make comparisons).
When power density is identical, mesoporous ZnCo2O4Nanometer sheet@NiCo2O4The energy density ratio ZnCo of nano wire2O4Nanometer sheet has significantly
It improves.Illustrate mesoporous ZnCo2O4Nanometer sheet@NiCo2O4The component synergistic effect of nanowire composite structures significantly improves electrode
Specific capacitance, cyclical stability, energy density and the power density of material.
Embodiment 3
A kind of mesoporous ZnCo2O4Nanometer sheet@NiCo2O4The preparation method of nanowire composite, includes the following steps：
(1) by 1mmol ZnSO4·7H2O, 2mmol CoSO4·7H2O and 1mmol tetrabutylammonium bromide is dissolved in successively
In 40mL deionized waters, 2mmol NaHCO are then added3, 28min is persistently stirred, solution A is obtained.Solution A is transferred to 50mL
Polytetrafluoroethylene (PTFE) be liner reaction kettle in, the nickel foam of the 2 × 3cm anticipated (is first used into the immersion of 6M dilute hydrochloric acid
10min removes the oxidation film of outer layer, is then cleaned with deionized water) tiltedly it is placed in solution, it seals and heats 10h at 180 DEG C,
Cooled to room temperature.The nickel foam deionized water and absolute ethyl alcohol for covering sample are respectively washed 3 times, and 60 DEG C of vacuum drying chambers are placed in
Middle dry 7h.
(2) by 0.1mmol Ni (NO3)2·6H2O, 0.2mmol Co (NO3)2·6H2O and 0.1mmol tetrabutyl phosphonium bromides
Ammonium is dissolved in successively in 40mL deionized waters, and 0.2mmol NaHCO are then added3, 20min is persistently stirred, solution B is obtained.It will
Solution B is transferred in the reaction kettle that 50mL polytetrafluoroethylene (PTFE) is liner, and the nickel foam of above-mentioned covering sample is tiltedly placed on solution
In, it seals and heats 8h, cooled to room temperature at 180 DEG C.Cover the nickel foam deionized water and absolute ethyl alcohol of sample
It respectively washes 3 times, is placed in 60 DEG C of vacuum drying chambers dry 8h.Later, the nickel foam for covering sample is placed in muffle furnace with 5 DEG C
min-1Rate be warming up to 400 DEG C calcining 2h.
Embodiment 4
A kind of mesoporous ZnCo2O4Nanometer sheet@NiCo2O4The preparation method of nanowire composite, includes the following steps：
(1) by 1mmol ZnSO4·7H2O, 2mmol CoSO4·7H2O and 1mmol tetrabutylammonium bromide is dissolved in successively
In 40mL deionized waters, 2mmol NaHCO are then added3, 20min is persistently stirred, solution A is obtained.Solution A is transferred to 50mL
Polytetrafluoroethylene (PTFE) be liner reaction kettle in, the nickel foam of the 2 × 3cm anticipated (is first used into the immersion of 6M dilute hydrochloric acid
10min removes the oxidation film of outer layer, is then cleaned with deionized water) tiltedly it is placed in solution, it seals and heats 7h at 180 DEG C,
Cooled to room temperature.The nickel foam deionized water and absolute ethyl alcohol for covering sample are respectively washed 3 times, and 60 DEG C of vacuum drying chambers are placed in
Middle dry 6h.
(2) by 0.1mmol Ni (NO3)2·6H2O, 0.2mmol Co (NO3)2·6H2O and 0.1mmol tetrabutyl phosphonium bromides
Ammonium is dissolved in successively in 40mL deionized waters, and 0.2mmol NaHCO are then added3, 25min is persistently stirred, solution B is obtained.It will
Solution B is transferred in the reaction kettle that 50mL polytetrafluoroethylene (PTFE) is liner, and the nickel foam of above-mentioned covering sample is tiltedly placed on solution
In, it seals and heats 8h, cooled to room temperature at 180 DEG C.Cover the nickel foam deionized water and absolute ethyl alcohol of sample
It respectively washes 3 times, is placed in 60 DEG C of vacuum drying chambers dry 12h.Later, the nickel foam for covering sample is placed in muffle furnace with 5 DEG C
min-1Rate be warming up to 400 DEG C calcining 3h.
Claims (9)
1. a kind of mesoporous ZnCo2O4Nanometer sheet@NiCo2O4The preparation method of nanowire composite, which is characterized in that the preparation
Method includes the following steps：
（1）By ZnSO4·7H2O、CoSO4·7H2O, tetrabutylammonium bromide and NaHCO3Dissolving in deionized water, stirs and evenly mixs,
Solution A is obtained, solution A is transferred in reaction kettle, nickel foam is tiltedly placed in solution, sealing, heating reaction naturally cool to
Room temperature, washing, drying, obtains the nickel foam of presoma；
（2）By Ni (NO3)2·6H2O、Co(NO3)2·6H2O, tetrabutylammonium bromide and NaHCO3Dissolving in deionized water, is stirred
Mixing obtains solution B, by solution B transfer reaction kettle, by step（1）The nickel foam of preparation is tiltedly placed in solution, and sealing adds
Thermal response, cooled to room temperature are washed, dry, and calcining obtains mesoporous ZnCo2O4Nanometer sheet@NiCo2O4Nano wire composite wood
Material；
Step（1）Middle ZnSO4·7H2O、CoSO4·7H2O, tetrabutylammonium bromide and NaHCO3Molar ratio be 1:2:1:2.
2. preparation method according to claim 1, which is characterized in that step（1）Middle tetrabutylammonium bromide is in solution A
A concentration of 0.025M.
3. preparation method according to claim 1, which is characterized in that step（1）Described in heat reaction, specially：180
6-12h is reacted at DEG C.
4. preparation method according to claim 1, which is characterized in that step（2）Middle Ni (NO3)2·6H2O、Co(NO3)2·
6H2O, tetrabutylammonium bromide and NaHCO3Molar ratio be 1:2:1:2.
5. preparation method according to claim 1 or 2, which is characterized in that tetrabutylammonium bromide is a concentration of in solution B
0.025M。
6. preparation method according to claim 1 or 2, which is characterized in that step（2）Described in heat reaction, specially：
6-12h is reacted at 180 DEG C of temperature.
7. preparation method according to claim 1 or 2, which is characterized in that step（2）Described in calcine, specially：Heating
5 DEG C of min of rate-1, 2-3h is calcined at 400 DEG C of temperature.
8. a kind of mesoporous ZnCo2O4Nanometer sheet@NiCo2O4Nanowire composite, which is characterized in that appointed according to claim 1-7
One the method is prepared.
9. mesoporous ZnCo prepared by a kind of any one of claim 1-7 preparation methods2O4Nanometer sheet@NiCo2O4Nano wire is multiple
Application of the condensation material as Asymmetric Supercapacitor electrode material.
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