CN107275123A - Cobalt acid nickel@tetra- vulcanizes two cobalts and closes nickel core-shell nano linear array composite and its preparation method and application - Google Patents
Cobalt acid nickel@tetra- vulcanizes two cobalts and closes nickel core-shell nano linear array composite and its preparation method and application Download PDFInfo
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- CN107275123A CN107275123A CN201710549943.3A CN201710549943A CN107275123A CN 107275123 A CN107275123 A CN 107275123A CN 201710549943 A CN201710549943 A CN 201710549943A CN 107275123 A CN107275123 A CN 107275123A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 67
- 239000011258 core-shell material Substances 0.000 title claims abstract description 52
- 235000013495 cobalt Nutrition 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 21
- 239000010941 cobalt Substances 0.000 title claims abstract description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000002253 acid Substances 0.000 title claims description 13
- 229910005949 NiCo2O4 Inorganic materials 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000006260 foam Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000002815 nickel Chemical class 0.000 claims abstract description 16
- 238000004073 vulcanization Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000002070 nanowire Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 229910017709 Ni Co Inorganic materials 0.000 claims abstract description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 230000020477 pH reduction Effects 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 11
- 229910003267 Ni-Co Inorganic materials 0.000 claims description 8
- 229910003262 Ni‐Co Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000003491 array Methods 0.000 claims 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 229910003266 NiCo Inorganic materials 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 21
- 230000004087 circulation Effects 0.000 description 8
- 238000001514 detection method Methods 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 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
- H01G11/84—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
-
- 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
- H01G11/24—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
-
- 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
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
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- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Vulcanize two cobalts the invention discloses a kind of sour nickel@tetra- of cobalt and close nickel core-shell nano linear array composite and its preparation method and application, the preparation method includes：1) nickel foam is subjected to acidification；2) nickel foam after acidification is placed in the reaction solution of closing and carries out hydro-thermal reaction, then cleaned, dry so that Ni Co compound precursors are made, the washing of Ni Co compounds precursor, dry, calcining are then obtained into NiCo2O4 nano-wire array materials；3) by NiCo2O4 nano-wire array materials, sulfide and water carry out vulcanization reaction, then wash reaction product, dry obtained NiCo2O4@NiCo2S4Core-shell nano linear array composite；Wherein, reaction solution contains nickel salt, cobalt salt, ammonium salt, urea and water.Pass through NiCo made from this method2O4@NiCo2S4Core-shell nano linear array has excellent capacitance, specific capacitance and stability.
Description
Technical field
The present invention relates to core-shell composite material, in particular it relates to which cobalt acid nickel@tetra- vulcanizes two cobalts and closes nickel core-shell nano linear array
Composite and its preparation method and application.
Background technology
Due to the consumption and the pollution of environment of the energy, tap a new source of energy great asking of having become that the world in recent years faces
Topic.In order to meet ever-increasing energy demand, it is necessary to research and develop that power is big, the green energy resource storage device of excellent in stability, and
Ultracapacitor is exactly one of optimal green energy resource storage material.Ultracapacitor has the operating voltage and excellent of safety
Chemical property, so as to be widely used in the research of green energy-storing equipment.
However, traditional ultracapacitor often has relatively low energy density, bad cyclical stability and low power
Forthright the shortcomings of, therefore the resistance and obstacle that the popularization for the technology of ultracapacitor is caused.
The content of the invention
It is an object of the invention to provide a kind of sour nickel@tetra- of cobalt vulcanize two cobalts close nickel core-shell nano linear array composite and its
Preparation method and application, pass through NiCo made from this method2O4@NiCo2S4Core-shell nano linear array have excellent capacitance,
Specific capacitance and stability, while the NiCo2O4@NiCo2S4Core-shell nano linear array can be used as ultracapacitor or lithium-ion electric
The electrode material in pond is used；In addition, the preparation method process is simply novel, raw material is easy to get, with low cost.
To achieve these goals, the invention provides vulcanize two cobalts the invention provides a kind of sour nickel@tetra- of cobalt to close nickel core
The preparation method of shell nano-wire array composite, including：
1) nickel foam is subjected to acidification；
2) nickel foam after acidification is placed in the reaction solution of closing and carries out hydro-thermal reaction, then clean, dry with
Ni-Co compound precursors are made, the washing of Ni-Co compounds precursor, dry, calcining are then obtained into NiCo2O4 nano wires
Array material；
3) by NiCo2O4 nano-wire array materials, sulfide and water carry out vulcanization reaction, are then washed reaction product
Wash, dry obtained NiCo2O4@NiCo2S4Core-shell nano linear array composite；
Wherein, reaction solution contains nickel salt, cobalt salt, ammonium salt, urea and water.
Vulcanize the preparation side that two cobalts close nickel core-shell nano linear array composite present invention also offers a kind of sour nickel@tetra- of cobalt
Method, cobalt acid nickel@tetra- vulcanizes two cobalts conjunction nickel core-shell nano linear array composite and is prepared by above-mentioned preparation method.
Vulcanize two cobalts invention further provides a kind of sour nickel@tetra- of above-mentioned cobalt and close nickel core-shell nano linear array composite wood
Expect the application in ultracapacitor.
In the above-mentioned technical solutions, the present invention is defoamed the oxide of nickel surface by acid treatment first, then will be compared with
Hydro-thermal reaction being carried out in the environment of closing with nickel salt, cobalt salt, ammonium salt, urea for pure nickel foam and then generating Ni-Co answering
Compound precursor, then obtains NiCo by sample calcining2O4Nano-wire array, finally using the sulfurization of sulfide with obtained
NiCo2O4@NiCo2S4Core-shell nano linear array.
Obtained NiCo is caused by the synergy of above steps2O4@NiCo2S4Core-shell nano linear array has excellent
Different capacitance, specific capacitance and stability, wherein, in 2Ag-1Under current density, NiCo2O4@NiCo2S4Core-shell nano linear array
The specific capacitance of row can reach 3176Fg-1；After 15000 times circulate, NiCo2O4@NiCo2S4The electricity of core-shell nano linear array
Appearance remains to keep more stable；Meanwhile, the NiCo2O4@NiCo2S4Core-shell nano linear array can be used as ultracapacitor or lithium
The electrode material of ion battery is used；In addition, the preparation method process is simple, raw material is easy to get, with low cost.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for 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：
SEM (SEM) figure that Fig. 1 is A1 in detection example 1；
Transmission electron microscope (TEM) figure that Fig. 2 is A1 in detection example 1；
X-ray diffraction pattern (XRD) figure that Fig. 3 is A1 in detection example 1；
Fig. 4 is AC impedance curve maps of the A1 before circulation and after 15000 circle circulations in application examples 1；
Fig. 5 is the cyclic voltammetry curve figure of A1 in application examples 1；
Fig. 6 is constant current charge-discharge curve maps of the A1 under different current densities in application examples 1；
Fig. 7 is that A1 is 6Ag in current density in application examples 1-1When circulation-specific capacitance curve map.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
Vulcanize the preparation side that two cobalts close nickel core-shell nano linear array composite the invention provides a kind of sour nickel@tetra- of cobalt
Method, including：
1) nickel foam is subjected to acidification；
2) nickel foam after acidification is placed in the reaction solution of closing and carries out hydro-thermal reaction, then clean, dry with
Ni-Co compound precursors are made, the washing of Ni-Co compounds precursor, dry, calcining are then obtained into NiCo2O4 nano wires
Array material；
3) by NiCo2O4 nano-wire array materials, sulfide and water carry out vulcanization reaction, are then washed reaction product
Wash, dry obtained NiCo2O4@NiCo2S4Core-shell nano linear array composite；
Wherein, reaction solution contains nickel salt, cobalt salt, ammonium salt, urea and water.
In the step 1 of above-mentioned preparation method) in, acid treatment can be carried out using various ways, but in order that nickel foam
The oxide removal on surface it is more thorough, it is preferable that in step 1) in, acid treatment is：Nickel foam is placed in acid solution and carried out
It is ultrasonically treated, then cleaned with water.
Wherein, ultrasonically treated concrete mode can be selected in wide scope, but in order that the oxygen of foam nickel surface
It is more thorough that compound is removed, it is preferable that ultrasonically treated at least to meet following condition：Processing time is 15-25min, processing temperature
Spend for 15-35 DEG C.
Meanwhile, the species of acid solution can be selected in wide scope, but in order that the oxide removal of foam nickel surface
It is more thorough, it is preferable that acid solution be hydrochloric acid solution, sulfuric acid solution or phosphoric acid solution, and acid solution concentration be 1.5-
2.5mol/L。
In addition, the time of water cleaning can select in wide scope, but in order that the oxide of foam nickel surface is gone
That removes is more thorough, it is preferable that the time of water cleaning is 8-15min.
In the present invention, the specification of nickel foam can be selected in wide scope, but in order that nickel foam and others
Reactant fully can contact to improve reaction efficiency, it is preferable that the specification of nickel foam is：A length of 1.5-2.5.m, it is a width of
2.5-3.5cm, thickness is 0.5-1.5mm, and weight is 0.1-0.2g.
In the step 2 of above-mentioned preparation method) in, the consumption of each material can be selected in wide scope, but in order that
Obtained NiCo2O4@NiCo2S4Core-shell nano linear array has more excellent capacitance, specific capacitance and stability, it is preferable that
Step 2) in, in reaction solution, nickel salt, cobalt salt, ammonium salt, the mole ratio of urea are 1：(1-3)：(5-8)：(10-15).
In the step 2 of above-mentioned preparation method) in, the consumption of water can be selected in wide scope, but in order that be made
NiCo2O4@NiCo2S4Core-shell nano linear array have more excellent capacitance, specific capacitance and stability, it is preferable that nickel salt with
The amount ratio of water is 1mmol：(20-50mL).
In the step 2 of above-mentioned preparation method) in, the actual conditions of hydro-thermal reaction can be selected in wide scope, still
In order that obtained NiCo2O4@NiCo2S4Core-shell nano linear array has more excellent capacitance, specific capacitance and stability, excellent
Selection of land, in step 2) in, hydro-thermal reaction at least meets following condition：Reaction temperature is 110-130 DEG C, and the reaction time is 4-6h.
In the step 2 of above-mentioned preparation method) in, the actual conditions of calcining can be selected in wide scope, but in order to
Make obtained NiCo2O4@NiCo2S4Core-shell nano linear array has more excellent capacitance, specific capacitance and stability, it is preferable that
Calcining at least meets following condition：Calcining heat is 310-330 DEG C, and calcination time is 1.5-3h.
In the step 2 of above-mentioned preparation method) in, nickel salt, cobalt salt, the specific species of ammonium salt can be selected in wide scope
Select, but in order that obtained NiCo2O4@NiCo2S4Core-shell nano linear array has more excellent capacitance, specific capacitance and steady
It is qualitative, it is preferable that in step 2) in, nickel salt is selected from least one of nickel nitrate, nickel sulfate and nickel chloride, and cobalt salt is selected from nitric acid
At least one of cobalt, cobaltous sulfate and cobalt chloride, ammonium salt are selected from least one of ammonium fluoride and ammonium chloride.
In the step 3 of above-mentioned preparation method) in, the consumption of each material can be selected in wide scope, but in order that
Obtained NiCo2O4@NiCo2S4Core-shell nano linear array has more excellent capacitance, specific capacitance and stability, it is preferable that
Step 3) in, the nickel salt relative to 1mmol, the consumption of sulfide is 0.6-1mmol.
In the step 3 of above-mentioned preparation method) in, the consumption of water can be selected in wide scope, but in order that be made
NiCo2O4@NiCo2S4Core-shell nano linear array has more excellent capacitance, specific capacitance and stability, it is preferable that in step
3) in, the nickel salt relative to 1mmol, the consumption of water is 20-50mL.
In the step 3 of above-mentioned preparation method) in, the specific species of sulfide can be selected in wide scope, but be
Make obtained NiCo2O4@NiCo2S4Core-shell nano linear array has more excellent capacitance, specific capacitance and stability, preferably
Ground, sulfide is selected from vulcanized sodium or potassium sulfide.
In the step 3 of above-mentioned preparation method) in, the actual conditions of vulcanization reaction can be selected in wide scope, still
In order that obtained NiCo2O4@NiCo2S4Core-shell nano linear array has more excellent capacitance, specific capacitance and stability, excellent
Selection of land, in step 3) in, vulcanization reaction at least meets following condition：Reaction temperature is 105-115 DEG C, and the reaction time is 4-12h.
In the step 2 of above-mentioned preparation method) -3) in, dry actual conditions can be selected in wide scope, but be
Make obtained NiCo2O4@NiCo2S4Core-shell nano linear array has more excellent capacitance, specific capacitance and stability, preferably
Ground, in step 2) -3) in, drying at least meets following condition：Drying temperature is 50-70 DEG C, and drying time is 12-24h；It is more excellent
Selection of land, is dried and is carried out using vacuum drying mode.
In the step 2 of above-mentioned preparation method) -3) in, the actual conditions of washing can be selected in wide scope, but be
Make obtained NiCo2O4@NiCo2S4Core-shell nano linear array has more excellent capacitance, specific capacitance and stability, preferably
Ground, in step 2) -3) in, washing is passed sequentially through is cleaned 2-4 times with deionized water and ethanol.
Vulcanize the preparation side that two cobalts close nickel core-shell nano linear array composite present invention also offers a kind of sour nickel@tetra- of cobalt
Method, cobalt acid nickel@tetra- vulcanizes two cobalts conjunction nickel core-shell nano linear array composite and is prepared by above-mentioned preparation method.
In the present invention, two cobalts of the sour vulcanizations of nickel@tetra- of cobalt conjunction nickel core-shell nano linear array composite property can be wide
In the range of select, but in order that obtained NiCo2O4@NiCo2S4Core-shell nano linear array has more excellent electrochemistry
Can, it is preferable that cobalt acid nickel@tetra-, which vulcanizes two cobalts and closes the chemical property of nickel core-shell nano linear array composite, is：Current density
For 2Ag-1When, specific capacitance is 3176Fg-1More than.
Vulcanize two cobalts invention further provides a kind of sour nickel@tetra- of above-mentioned cobalt and close nickel core-shell nano linear array composite wood
Expect the application in ultracapacitor.
The present invention will be described in detail by way of examples below.
Embodiment 1
1) pretreatment of nickel foam：At 25 DEG C, by nickel foam, (specification is 2cm × 2cm, and thickness is 1.3mm, and weight is
Ultrasound 20min in 2mol/L hydrochloric acid solution 0.1488g) is immersed in, then 10min is cleaned with deionized water；
2) by 1mmol Ni (NO3)2·6H2O、2mmol Co(NO3)2·6H2O、6mmol NH4F and 12mmol urea
It is dissolved in 35ml deionized waters and stirs 30min formation mixed solutions, the nickel foam after acidification is then immersed in mixing
In solution, then reaction system is transferred in 50ml reactors and progress hydro-thermal reaction (reacting 5h at 120 DEG C) is closed, cooling
Ni-Co compound precursors are taken out afterwards, are washed respectively with deionized water and absolute ethyl alcohol 3 times, 60 DEG C of drying, then at 320 DEG C
Calcining 2h can be prepared by NiCo to be made2O4Nano-wire array material；
3) 0.8mmol vulcanized sodium is dissolved in 35ml deionized waters, then by above-mentioned NiCo2O4Nano-wire array material soaks
Not in the solution, then reaction system is transferred in 50ml reactors and closes progress vulcanization reaction (reacting 8h at 110 DEG C)；
After vulcanization reaction terminates, question response kettle is cooled to 25 DEG C, takes out nickel foam, is washed 3 times with deionized water and absolute ethyl alcohol successively,
60 DEG C of dry 12h are placed in afterwards obtains NiCo2O4@NiCo2S4Core-shell nano linear array composite A 1.
Embodiment 2
Method according to embodiment 1 carries out that NiCo is made2O4@NiCo2S4Core-shell nano linear array composite A 2 is different
Be：Nickel foam meets following condition：Specification is 2cm × 3cm, and thickness is 1mm, and weight is 0.148g；Step 2) Ni in solution
(NO3)2·6H2O、Co(NO3)2·6H2O、NH4The content of F and urea is respectively 1mmol, 2mmol, 5mmol and 10mmol；
Step 3) in the content of vulcanized sodium be 0.8mmol, the condition of vulcanization reaction is to react 4h at 110 DEG C.
Embodiment 3
Method according to embodiment 1 carries out that NiCo is made2O4@NiCo2S4Core-shell nano linear array composite A 3 is different
Be：Nickel foam meets following condition：Specification is 2cm × 4cm, and thickness is 0.8mm, and weight is 0.147g；Step 2) in solution
Ni(NO3)2·6H2O、Co(NO3)2·6H2O、NH4The content of F and urea be respectively 1mmol, 2mmol, 6mmol and
12mmol；Step 3) in the content of vulcanized sodium be 0.6mmol, the condition of vulcanization reaction is to react 8h at 110 DEG C.
Embodiment 4
Method according to embodiment 1 carries out that NiCo is made2O4@NiCo2S4Core-shell nano linear array composite A 4 is different
Be：Step 2) Ni (NO in solution3)2·6H2O、Co(NO3)2·6H2O、NH4The content of F and urea be respectively 1mmol,
2mmol, 6mmol and 12mmol；Step 3) in the content of vulcanized sodium be 0.8mmol, the condition of vulcanization reaction is to react at 110 DEG C
12h。
Embodiment 5
Method according to embodiment 1 carries out that NiCo is made2O4@NiCo2S4Core-shell nano linear array composite A 5 is different
Be：Nickel foam meets following condition：Specification is 2cm × 3cm, and thickness is 1.5mm, and weight is 0.1498g；Step 2) in solution
Ni(NO3)2·6H2O、Co(NO3)2·6H2O、NH4The content of F and urea be respectively 1mmol, 2mmol, 8mmol and
15mmol；Step 3) in the content of vulcanized sodium be 1.0mmol, the condition of vulcanization reaction is to react 12h at 110 DEG C.
Detect example 1
1) morphology analysis is carried out to A1 by SEM (SEM), as a result as shown in figure 1, showing that A1 is nucleocapsid
Nanostructured.
2) A1 is analyzed by transmission electron microscope (TEM), as a result as shown in Figure 2.Further demonstrate that A1 is
Nucleocapsid heterojunction structure.
3) A1 is detected by X-ray diffractometer (XRD), as a result as shown in figure 3, by Fig. 3 and JCPDS standard cards NO.73-
NiCo corresponding to 17022O4Diffraction maximum and the NiCo corresponding to JCPDS standard cards NO.43-14772S4Diffraction maximum it is complete
It is complete to coincide, so as to convincingly demonstrate A1 for NiCo2O4@NiCo2S4Core-shell nano linear array.
A2-A5 is detected according to above-mentioned identical method, is as a result shown, A2-A5 detection structure and A1 testing result base
Originally it is consistent.
Application examples 1
Test instrument is CHI660E electrochemical workstations (manufacture of Shanghai Chen Hua Instrument Ltd.) below.With
Lower test uses three-electrode system, wherein, by NiCo2O4@NiCo2S4Composite A 1, acetylene black, polytetrafluoroethylene (PTFE)
(PTFE) according to 8：1：1 weight is than obtained working electrode, using platinum electrode with full as to electrode, calomel electrode (SCE) work
For reference electrode；Electrolyte is used as using 3mol/L KOH solution.
1) electrochemical impedance spectroscopy is tested
Detect that working electrode ac impedance spectroscopy before and after the circle of circulation 15000 is contrasted by electrochemical impedance spectroscopy, as a result
As shown in figure 4, wherein, 1th curves represent the AC impedance curve of working electrode before the loop, 15000th curves represent work
Make AC impedance curve of the electrode after 15000 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.In the internal resistance that the intersection point of high frequency region impedance spectrum and real axis is working electrode, including active material is in itself
Resistance, the contact resistance of the resistance of electrolyte and active material and electrolyte.In high frequency region it can be found that working electrode is being followed
Curve approximation when before ring and after 15000 circulations, the curve of high frequency region before the loop with after circulation closer to more
The electrode material of excellent ultracapacitor, be indicated above A1 can as ultracapacitor electrode material.
2) cyclic voltammetry (CV) is tested
Respectively with 2mVs-1、10mV·s-1、20mV·s-1、40mV·s-1And 60mVs-1Sweep speed swept
Retouch, draw the cyclic voltammetry curve of working electrode as shown in figure 5, the potential range of the curve is 0-0.5V.Gone out by CV graphic calculations
Specific capacitance, i.e. NiCo2O4@NiCo2S4Core-shell nano linear array composite in 2mVs-1It is 5340F to sweep specific capacitance under speed
g-1, illustrate that A1 has the performance of excellent storage electricity.
Wherein, electric capacity calculation formula is：I is size of current, and v is sweeps speed, and △ V are
Electrical potential difference, m is the quality of sample on working electrode piece.
3) constant current charge-discharge (CP) is tested
Respectively in 2.0Ag-1、2.5A·g-1、3.0A·g-1、3.75A·g-1And 5.0Ag-1Lower progress constant current charge and discharge
Electro-detection, show that constant current charge-discharge curve of the working electrode under different current densities is as shown in Figure 6；Wherein, the curve is vertical
Coordinate is that voltage range is 0-0.5V.The specific capacitance discharge and recharge under different current densities is calculated by following equation.By filling
Electric discharge graphic calculation goes out specific capacitance, i.e. NiCo2O4@NiCo2S4Core-shell nano linear array composite in 2.0Ag-1Under current density
Specific capacitance is 3176Fg-1, illustrate that A1 has the performance of excellent storage electricity.
Wherein, electric capacity calculation formula is：Cm=(It)/(△ Vm), I are size of current, and t is discharge time, and △ V are
Electrical potential difference, m is the quality of sample on working electrode piece.
4) cycle performance is detected
In 60mVs-1Sweep speed under circulate 15000 times, obtain circulation-specific capacitance curve of working electrode, as a result
As shown in fig. 7, will termination capacity and initial capacity contrast understand, by 15000 times circulate after lifted compared with initial capacitance and
Tend towards stability, illustrate that A1 has excellent stability.
A2-A5 is detected according to above-mentioned identical method, is as a result shown, A2-A5 detection structure and A1 testing result base
Originally it is consistent.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
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 equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of sour nickel@tetra- of cobalt vulcanizes the preparation method that two cobalts close nickel core-shell nano linear array composite, it is characterised in that bag
Include：
1) nickel foam is subjected to acidification；
2) nickel foam after acidification is placed in the reaction solution of closing and carries out hydro-thermal reaction, then clean, dry with
Ni-Co compound precursors are made, Ni-Co compounds precursor washing, dry, calcining are then obtained into NiCo2O4 receives
Nanowire arrays material；
3) by the NiCo2O4 nano-wire array materials, sulfide and water carry out vulcanization reaction, are then washed reaction product
Wash, dry obtained NiCo2O4@NiCo2S4Core-shell nano linear array composite；
Wherein, the reaction solution contains nickel salt, cobalt salt, ammonium salt, urea and water.
2. preparation method according to claim 1, wherein, in step 1) in, the acid treatment is：The nickel foam is put
Carry out ultrasonically treated, then cleaned with water in acid solution；
Preferably, it is described ultrasonically treated at least to meet following condition：Processing time is 15-25min, and treatment temperature is 15-35 DEG C；
It is highly preferred that the acid solution is hydrochloric acid solution, sulfuric acid solution or phosphoric acid solution, and the concentration of the acid solution is 1.5-
2.5mol/L；
It is further preferred that the time of the water cleaning is 8-15min；
It is further preferred that the specification of the nickel foam is：A length of 1.5-2.5.m, a width of 2.5-3.5cm, thickness is 0.5-
1.5mm, weight is 0.1-0.2g.
3. preparation method according to claim 1, wherein, in step 2) in, in the reaction solution, the nickel salt, cobalt
Salt, ammonium salt, the mole ratio of urea are 1：(1-3)：(5-8)：(10-15)；
Preferably, the amount ratio of the nickel salt and water is 1mmol：(20-50mL).
4. preparation method according to claim 1, wherein, in step 2) in, the hydro-thermal reaction at least meets following bar
Part：Reaction temperature is 110-130 DEG C, and the reaction time is 4-6h；
Preferably, the calcining at least meets following condition：Calcining heat is 310-330 DEG C, and calcination time is 1.5-3h.
5. the preparation method according to any one in claim 1-4, wherein, in step 2) in, the nickel salt is selected from nitre
At least one of sour nickel, nickel sulfate and nickel chloride, the cobalt salt are selected from least one of cobalt nitrate, cobaltous sulfate and cobalt chloride, institute
State ammonium salt and be selected from least one of ammonium fluoride and ammonium chloride.
6. the preparation method according to any one in claim 1-4, wherein, in step 3) in, the institute relative to 1mmol
Nickel salt is stated, the consumption of the sulfide is 0.6-1mmol；
Preferably, in step 3) in, the nickel salt relative to 1mmol, the consumption of the water is 20-50mL；
It is highly preferred that the sulfide is selected from vulcanized sodium.
7. preparation method according to claim 6, wherein, in step 3) in, the vulcanization reaction at least meets following bar
Part：Reaction temperature is 105-115 DEG C, and the reaction time is 4-12h.
8. preparation method according to claim 6, wherein, in step 2) -3) in, the drying at least meets following bar
Part：Drying temperature is 50-70 DEG C, and drying time is 12-24h；
Preferably, the drying is carried out using vacuum drying mode；
It is highly preferred that in step 2) -3) in, the washing is passed sequentially through is cleaned 2-4 times with deionized water and ethanol.
9. a kind of sour nickel@tetra- of cobalt vulcanizes the preparation method that two cobalts close nickel core-shell nano linear array composite, it is characterised in that institute
The cobalt sour vulcanizations of nickel@tetra- two cobalts conjunction nickel core-shell nano linear array composite is stated to pass through described in any one in claim 1-8
Preparation method is prepared；
Preferably, the chemical property of two cobalts of the sour vulcanizations of nickel@tetra- of cobalt conjunction nickel core-shell nano linear array composite is：Electric current
Density is 2Ag-1When, specific capacitance is 3176Fg-1More than.
10. a kind of sour nickel@tetra- of cobalt as claimed in claim 9 vulcanizes two cobalts and closes the super electricity of nickel core-shell nano linear array composite
Application in container or lithium battery.
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