CN108364795A - A kind of two-layer nanowire hierarchical structure NiCo2O4-ZnCo2O4 combination electrode materials haveing excellent performance - Google Patents
A kind of two-layer nanowire hierarchical structure NiCo2O4-ZnCo2O4 combination electrode materials haveing excellent performance Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 42
- 229910003119 ZnCo2O4 Inorganic materials 0.000 title claims abstract description 36
- 239000002070 nanowire Substances 0.000 title claims abstract description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000009826 distribution Methods 0.000 claims abstract description 4
- 239000006260 foam Substances 0.000 claims description 9
- 229910005949 NiCo2O4 Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000002195 synergetic effect Effects 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 3
- 235000012149 noodles Nutrition 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 241000209094 Oryza Species 0.000 claims 2
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 9
- 239000003990 capacitor Substances 0.000 description 7
- 230000005611 electricity Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- -1 Transition Metal Sulfur Compound Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 241000797947 Paria Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- 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
Abstract
The present invention discloses a kind of two-layer nanowire hierarchical structure NiCo haveing excellent performance2O4‑ZnCo2O4Combination electrode material belongs to new energy field of storage.The present invention uses foamed nickel supported NiCo prepared by one step hydro thermal method combination calcine technology2O4‑ZnCo2O4There is combination electrode material novel two-layer nanowire hierarchical structure, the laterally staggered distribution of thin nano wire of 15 30nm of internal layer diameter, the adjacent thick nano wire head of outer layer to merge to form nano line cluster, the thick nano wire that vertical-growth goes out at the top of it.The combination electrode material has excellent chemical property：It is 2A g that quality specific capacitance knead dough, which accumulates specific capacitance in current density,‑1When, respectively 3087.1F g‑1With 5.56F cm‑2；In 20A g‑1When, respectively 2205.8F g‑1With 3.97F cm‑2, the specific capacitance conservation rate of 2000 cycles is 101.0%.
Description
Technical field
The present invention relates to a kind of two-layer nanowire hierarchical structure NiCo haveing excellent performance2O4-ZnCo2O4Combination electrode material,
Belong to new energy field of storage.
Background technology
Face of mankind nowadays fossil energy increasingly shortage, environment worsening serious problems, develop it is clean renewable
Novel energy conversion it is extremely urgent with storage device.Ultracapacitor is a kind of new between traditional capacitor and battery
Type energy-storage travelling wave tube, has that charge/discharge rates are fast, power density is high, have extended cycle life with advantages of environment protection and as in the industry
One bright spot, the energy regenerating that enters the station in hybrid power integral new-energy passenger, rail traffic, online and energy storage in electric power network
It is all widely used using the intelligent start/stop system etc. of, car.Relative to battery, the energy density ratio of ultracapacitor
It is relatively low, and the specific capacitance for improving electrode material is to improve one of the effective way of super capacitor energy density.With super electricity
The continuous expansion of container application field, the research of electrode material for super capacitor is by the extensive concern of researcher.
According to energy storage mechnism difference, ultracapacitor can be divided into double layer capacitor and pseudocapacitors, and the latter's performance is better than
The former.Currently, the electrode material of pseudocapacitors mainly has transition metal oxide, transition metal hydroxide, Transition Metal Sulfur
Compound etc..With NiCo2O4For the ternary transition metal oxide of representative, due to having conduction more better than its single metal oxides
Property and more superior chemical property and by heat hold in both hands.
Researcher carries out ternary transition metal oxide, sulfide electrode material in the application of ultracapacitor a large amount of
Research work.As Cai et al. prepares NiCo using hydro-thermal method2O4Nano-chip arrays electrode is 5mA cm in current density-2When,
Area specific capacitance and quality specific capacitance are respectively 2.61F cm-2With 1088F g-1(Daoping Cai,Songhua Xiao,
Dandan Wang, Bin Liu,Lingling Wang,Yuan Liu,Han Li,Yanrong Wang,Qiuhong Li,
Taihong Wang, Electrochimica Acta,2014,142,118–124).Patent CN103979618B, " one kind is super
The synthetic method of grade capacitor cobalt acid nickel nano material ", by CoSO4·7H2O、NiSO4·6H2Deionization is added with urea in O
In water, and glycerine is added and carries out hydro-thermal reaction, then in 300~400 DEG C of tube furnace calcining at constant temperature 3 hours, cobalt acid nickel is made
Nano material, specific capacitance 960F/g.Patent CN104465117A, a kind of " cobalt acid zinc@manganese dioxide nucleocapsid heterogeneous structural nanos
Pipe array material, preparation method and applications ", the electrode material maximum specific capacitance invented are 2458F/g.Huang et al. is adopted
ZnCo is prepared with electrostatic spinning combination coprecipitation2O4@NiCo2O4Nano line electrode is 1A g in current density-1When, than electricity
It is 1476F g to hold-1, 2000 cyclical stabilities are 98.9% (Yunpeng Huang, Yue-E.Miao, Hengyi Lu, and
Tianxi Liu, Chem.Eur.J.2015,21,1-10).India Anirban Maitra et al. prepare Zn- using hydro-thermal method
Fe-Co oxide nano threads are 1A g in current density-1When quality specific capacitance be 2587.4F g-1, 3000 times cycle after electricity
Appearance conservation rate is 95.5% (Anirban Maitra, Amit Kumar Das, Ranadip Bera, Sumanta Kumar
Karan, Sarbaranjan Paria, Suman Kumar Si, and Bhanu Bhusan Khatua, ACS
Appl.Mater.Interfaces,2017,9,5947-5958).Nanjing University Zhu et al. uses two steps on silver sputtering fabric
Hydro-thermal method is prepared by FeCo2S4–NiCo2S4Nanotube constitutes the composite material of tripod structure, is 5mA cm in current density-2When, area specific capacitance and quality specific capacitance are respectively for 3.5F cm-2With 1519F g-1, it is pure NiCo2S4Nano-tube array
12.5 times and pure FeCo2S4Nano-tube array 1.3 times (Jian Zhu, Shaochun Tang, Juan Wu, Xiling Shi,
Baogang Zhu,and Xiangkang Meng,Adv.Energy Mater.,2016,1601234).In conclusion ternary
The compound etc. of transition metal oxide and its nucleocapsid, multicomponent transition metal oxide, ternary transition metal sulfide
It is expected to the ideal electrode material as ultracapacitor, thus becomes current research hotspot.
Recent years, transition metal oxide achieve certain achievement as the research of electrode of super capacitor.
NiCo2O4、 ZnCo2O4The ternary transition metal oxide of equal spinel structures is capable of providing due to good electric conductivity than it
The more rich redox reaction of single metal oxides, specific capacitance are improved to some extent, but still cannot meet it is current right
Needs with high-energy density super capacitor.Ternary transition metal oxide nucleocapsid structure electrode material, due to fully sharp
With the synergistic effect of core-shell structure copolymer materials at two layers, the specific capacitance of electrode material is further increased, but it prepares and generally uses two step hydro-thermals
The methods of method or one step hydro thermal method combination electro-deposition, then carry out calcination processing again, and preparation process is relatively cumbersome.And by two kind three
Research of the combination electrode material that element/transition metal oxide is constituted for ultracapacitor is less, currently almost without relevant
Document report.The present invention prepares the NiCo haveing excellent performance using simple one step hydro thermal method combination calcine technology2O4-ZnCo2O4
Combination electrode material has important application value.
Invention content
It is an object of the invention to be directed to existing electrode material there are the problem of, provide a kind of preparation process it is relatively easy,
The two-layer nanowire hierarchical structure NiCo haveing excellent performance2O4-ZnCo2O4Combination electrode material, specific invention content are：
(1) using nickel foam as conductive substrate, Ni (NO3)2·6H2O、Zn(NO3)2·6H2O、Co(NO3)2·6H2O、CO
(NH2)2And NH4F is raw material, and NiCo is prepared using one step hydro thermal method2O4-ZnCo2O4The precursor of combination electrode material, calcines it
Precursor obtains Ni nanoparticle Co2O4-ZnCo2O4Combination electrode material.
(2) the foamed nickel supported Ni nanoparticle Co prepared by2O4-ZnCo2O4Combination electrode material is uniformly slightly received by outer layer
What the thin nano wire of rice noodles and internal layer was constituted, there is novel two-layer nanowire hierarchical structure.The a diameter of 15-30nm's of internal layer is thin
The laterally staggered distribution of nano wire, a diameter of 60-90nm of outer layer, adjacent thick nano wire head merge, and being formed has surely
Determine the nano line cluster of structure, and vertical-growth goes out the thick nano wire with round end at the top of it.It is directly grown in nickel foam substrate
Nano wire there is good electric conductivity, have a large amount of hole between nano wire, be convenient for electrolyte in electrochemical reaction process
The infiltration and exudation of intermediate ion, this for combination electrode material there is excellent electrochemical performance to provide important structural condition.
(3) the foamed nickel supported Ni nanoparticle Co prepared by2O4-ZnCo2O4Combination electrode material is due to NiCo2O4And ZnCo2O4
Synergistic effect and the novel two-layer nanowire hierarchical structure of two kinds of components and there is excellent chemical property, mass ratio electricity
Appearance and area specific capacitance are 2Ag in current density-1When respectively 3087.1F g-1With 5.56F cm-2；It is in current density
20Ag-1When respectively 2205.8F g-1With 3.97F cm-2, multiplying power 71.5%, 2000 times the quality recycled compares capacity retention
It is 101.0%.
Description of the drawings
Fig. 1 is prepared NiCo2O4-ZnCo2O4The SEM stereoscan photographs of combination electrode material.(a) low power number
SEM photograph；(b) high magnification numbe SEM photograph.
Fig. 2 is prepared NiCo2O4-ZnCo2O4The Surface scan photo of combination electrode material.
Fig. 3 is prepared NiCo2O4-ZnCo2O4The XRD spectrum of combination electrode material.
Fig. 4 is prepared NiCo2O4-ZnCo2O4The Electrochemical results of combination electrode material.(a) different scanning speed
Cyclic voltammetry curve under degree；(b) charging and discharging curve under different current densities；(c) the mass ratio electricity under different current densities
Hold and area specific capacitance curve；(d) impedance spectrum.
Fig. 5 is prepared NiCo2O4-ZnCo2O4Combination electrode material is 20Ag in current density-1When pass through 2000 times
The quality of cycle is than capacitance variations figure.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
(1) nickel foam is immersed in 15min in the hydrochloric acid solution of 3mol/L then to go successively to remove oxide on surface
Respectively it is cleaned by ultrasonic in ionized water and absolute ethyl alcohol 3 times, obtains clean nickel foam；
(2) it is 0.67 by molar ratio：0.33：2：5：2.1 Ni (NO3)2·6H2O、Zn(NO3)2·6H2O、 Co
(NO3)2·6H2O、CO(NH2)2And NH4F, which is dissolved in deionized water, obtains mixed solution, wherein Ni2+And Zn2+Total concentration be
20mM；
(3) mixed solution obtained by (2) is transferred in reaction kettle, and clean nickel foam is added thereto, put after sealing
Enter in drying box, the hydro-thermal reaction 12h at 120 DEG C, it is clear in deionized water and absolute ethyl alcohol successively after cooled to room temperature
Wash it is each three times, and the dry 12h at 60 DEG C obtains presoma；
(4) precursor obtained is calcined into 2h at 400 DEG C in air atmosphere, obtains foamed nickel supported two-layer nanowire point
Level structure NiCo2O4-ZnCo2O4Combination electrode material.
Fig. 1 is prepared NiCo2O4-ZnCo2O4The SEM photograph of combination electrode material shines from Fig. 1 (a) low power numbers SEM
Piece, which can be seen that foam nickel surface, has one layer of uniform, intensive covering, coarse surface to look like fluffy, soft grass
Level ground is conducive to the infiltration and exudation of electrolyte.Can be seen that the covering from 1 (b) high magnification numbe SEM photograph is by the thin of internal layer
Uniformly thick nano wire is constituted for nano wire and outer layer.The laterally staggered distribution of thin nano wire of a diameter of 15-30nm of internal layer, outer layer
A diameter of 60-90nm, adjacent thick nano wire head merge, and form the nano line cluster with rock-steady structure, and at it
Top vertical-growth goes out one or a few thick nano wire with round end.There is a large amount of hole between the nano wire of the double-deck hierarchical structure
Gap is convenient for the infiltration and exudation of electrolyte intermediate ion in electrochemical reaction process；In addition, nano wire is directly grown in nickel foam
On substrate, there is good electric conductivity, be convenient for the quick transmission of electronics, this has excellent electrochemical performance for combination electrode material
Important structural condition is provided.Fig. 2 is prepared NiCo2O4-ZnCo2O4The Surface scan photo of compound, show Ni, Zn and
Co is uniformly distributed, it was demonstrated that prepared electrode material may be NiCo2O4-ZnCo2O4Compound.Fig. 3 is prepared
NiCo2O4-ZnCo2O4The XRD spectrum of combination electrode material, it can be seen from the figure that diffraction maximum correspond to respectively crystal face (111),
(220), (311), (511) and (440), with NiCo2O4Standard card PDF 20-0781 and ZnCo2O4PDF 23-1390 be
Consistent, NiCo2O4And ZnCo2O4The corresponding angle of diffraction of diffraction maximum differs very little and is difficult to differentiate between, in the face power spectrum in conjunction with Fig. 2
Ni, Zn and Co are uniformly distributed, and are determined as the NiCo with spinel structure2O4-ZnCo2O4Compound.Other three strong peak (*)
It is the diffraction maximum of nickel foam substrate.
Fig. 4 is prepared NiCo2O4-ZnCo2O4The electrochemical property test result of combination electrode material.Fig. 4 (a) is
Cyclic voltammetry curve under different scanning speed, every curve have a pair of of redox peaks, show that fake capacitance occurs for electrode
Redox reaction.Fig. 4 (b) is the constant current charge-discharge curve under different current densities, and all curves have voltage platform, into one
Step shows the fake capacitance characteristic of electrode.It is 2Ag in current density-1When, the longest charge and discharge time reaches 1204.1s, illustrates that electrode has
There is higher capacity.Fig. 4 (c) is that the quality specific capacitance knead dough under different current densities accumulates specific capacitance curve, Ni nanoparticle Co2O4-
ZnCo2O4The quality specific capacitance knead dough product specific capacitance of combination electrode material is 2Ag in current density-1When, respectively 3087.1F
g-1With 5.56F cm-2；It is 20A g in current density-1When, respectively 2205.8F g-1With 3.97F cm-2, multiplying power is
71.5%, there is higher high rate performance.Fig. 4 (d) is the impedance spectrum of combination electrode material, and the curved portion of high frequency region has
The intercept of very little, contact impedance are 0.37 Europe, and the semicircle of very little shows small interfacial charge transfer impedance, the straight line portion of low frequency range
Dividing has larger slope, illustrates it with good electric conductivity.Fig. 5 is prepared NiCo2O4-ZnCo2O4Combination electrode material
In current density 20Ag-1For the quality recycled by 2000 times than capacitance variations, the conservation rate of quality specific capacitance is 101.0%.
It can be seen that prepared foamed nickel supported Ni nanoparticle Co2O4-ZnCo2O4Combination electrode material is due to NiCo2O4And ZnCo2O4Two
Synergistic effect and the novel two-layer nanowire hierarchical structure of kind of component and there is excellent chemical property.
The foregoing is merely the embodiments of electrode material of the present invention, are not intended to limit the invention, it is all the present invention spirit and
All any modification, equivalent and improvement made by within principle etc. should all contain within protection scope of the present invention.
Claims (3)
1. a kind of two-layer nanowire hierarchical structure NiCo haveing excellent performance2O4-ZnCo2O4Combination electrode material, it is characterised in that：Institute
Combination electrode material is stated with novel two-layer nanowire hierarchical structure, preparation process is：Using nickel foam as conductive substrate, Ni
(NO3)2·6H2O、Zn(NO3)2·6H2O、Co(NO3)2·6H2O、CO(NH2)2And NH4F is raw material, using one step hydro thermal method system
Standby NiCo2O4-ZnCo2O4The precursor of combination electrode material calcines its precursor and obtains Ni nanoparticle Co2O4-ZnCo2O4Compound electric
Pole material.
2. a kind of two-layer nanowire hierarchical structure NiCo haveing excellent performance according to claim 12O4-ZnCo2O4Compound electric
Pole material, which is characterized in that novel two-layer nanowire hierarchical structure is uniformly slightly received by the thin nano wire and outer layer of internal layer
Rice noodles are constituted, the laterally staggered distribution of thin nano wire of a diameter of 15-30nm of internal layer, a diameter of 60-90nm of outer layer, adjacent thick are received
Rice noodles head merges, and forms the nano line cluster with rock-steady structure, and vertical-growth goes out one or a few at the top of it
Thick nano wire with round end has a large amount of hole between nano wire.
3. a kind of two-layer nanowire hierarchical structure NiCo haveing excellent performance according to claim 12O4-ZnCo2O4Compound electric
Pole material, which is characterized in that combination electrode material is due to NiCo2O4And ZnCo2O4The synergistic effect of two kinds of components and novel double
Layer nano wire hierarchical structure and have excellent chemical property, quality specific capacitance knead dough accumulate specific capacitance current density be 2A
g-1When, respectively 3087.1F g-1With 5.56F cm-2, it is 20A g in current density-1When, respectively 2205.8F g-1With
3.97F cm-2, multiplying power 71.5%, 2000 quality recycled are 101.0% than capacity retention.
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| CN201810131872.XA CN108364795B (en) | 2018-02-09 | 2018-02-09 | A kind of two-layer nanowire hierarchical structure NiCo2O4-ZnCo2O4 combination electrode material haveing excellent performance |
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| CN201810131872.XA CN108364795B (en) | 2018-02-09 | 2018-02-09 | A kind of two-layer nanowire hierarchical structure NiCo2O4-ZnCo2O4 combination electrode material haveing excellent performance |
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| CN108364795A true CN108364795A (en) | 2018-08-03 |
| CN108364795B CN108364795B (en) | 2019-11-15 |
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Cited By (3)
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| CN109273283A (en) * | 2018-09-28 | 2019-01-25 | 哈尔滨商业大学 | A kind of preparation method of nickel foam/molybdic acid nickel cobalt acid zinc laminated film |
| CN111584249A (en) * | 2020-06-28 | 2020-08-25 | 西北师范大学 | Preparation method of cobalt molybdate/nickel cobaltate composite material with three-dimensional flower-ball-shaped structure |
| CN113860389A (en) * | 2021-10-28 | 2021-12-31 | 中船动力(集团)有限公司 | Fe-Co-S nanotube array electrocatalytic material and preparation method thereof |
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| US20100181200A1 (en) * | 2009-01-22 | 2010-07-22 | Samsung Electronics Co., Ltd. | Transition metal/carbon nanotube composite and method of preparing the same |
| CN106328392A (en) * | 2016-09-23 | 2017-01-11 | 安徽师范大学 | Mesoporous ZnCo2O4 nanosheet@NiCo2O4 nanosheet composite material, preparation method and application |
| CN107240505A (en) * | 2017-06-09 | 2017-10-10 | 上海工程技术大学 | Electrode material for super capacitor Zn doping NiCo2O4Compound and preparation method |
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| US20100181200A1 (en) * | 2009-01-22 | 2010-07-22 | Samsung Electronics Co., Ltd. | Transition metal/carbon nanotube composite and method of preparing the same |
| CN106328392A (en) * | 2016-09-23 | 2017-01-11 | 安徽师范大学 | Mesoporous ZnCo2O4 nanosheet@NiCo2O4 nanosheet composite material, preparation method and application |
| CN107240505A (en) * | 2017-06-09 | 2017-10-10 | 上海工程技术大学 | Electrode material for super capacitor Zn doping NiCo2O4Compound and preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109273283A (en) * | 2018-09-28 | 2019-01-25 | 哈尔滨商业大学 | A kind of preparation method of nickel foam/molybdic acid nickel cobalt acid zinc laminated film |
| CN111584249A (en) * | 2020-06-28 | 2020-08-25 | 西北师范大学 | Preparation method of cobalt molybdate/nickel cobaltate composite material with three-dimensional flower-ball-shaped structure |
| CN113860389A (en) * | 2021-10-28 | 2021-12-31 | 中船动力(集团)有限公司 | Fe-Co-S nanotube array electrocatalytic material and preparation method thereof |
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