CN106098402B - A kind of CoNiSe for ultracapacitor2Nano-array material and preparation method thereof - Google Patents
A kind of CoNiSe for ultracapacitor2Nano-array material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 53
- 239000006260 foam Substances 0.000 claims abstract description 52
- 239000003990 capacitor Substances 0.000 claims abstract description 23
- 239000002071 nanotube Substances 0.000 claims abstract description 17
- 239000002077 nanosphere Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 8
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- -1 Transition metal selenides Chemical class 0.000 description 7
- 239000003792 electrolyte Substances 0.000 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 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000012827 research and development Methods 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000003346 selenoethers Chemical class 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of CoNiSe for ultracapacitor2Nano-array material and preparation method thereof.Preparation process includes：Nickel foam is pre-processed, the collector as electrode；Precursor nanosphere is first grown in foam nickel base；Then by precursor selenizing, you can obtain CoNiSe2Nano-array.Preparation method of the present invention is easy to operate, does not need complex device, of low cost；The CoNiSe of preparation2In nano array structure, nano-array is by CoNiSe2The surface of nanometer rods and nanotube composition, a diameter of 50 ~ 100nm of nanometer rods and nanotube, nanometer rods and nanotube is vesicular texture.CoNiSe produced by the present invention2Nano-array material is in 1 A g‑1Current density under show 1338F g‑1Height ratio capacity, while there is good high rate performance and superior electrochemical stability, be a kind of excellent electrode material for super capacitor.
Description
Technical field
The present invention relates to the field of electrode material for super capacitor, more particularly to a kind of transition gold for ultracapacitor
Belong to binary selenides electrode material and preparation method thereof.
Background technology
With the fast development of global economy, fossil energy constantly consumes, and environmental pollution increasingly sharpens, the future economy and society
A series of global problems of meeting sustainable development are increasingly paid high attention to by countries in the world.In this context, Ren Menzheng
Actively finding and developing various novel clean energy resourcies, such as solar energy, wind energy, tide energy, nuclear energy, biological energy source.In energy
Source domain, a kind of efficient, low cost of exploitation, long-life, environmental-friendly energy conversion and storage system have seemed increasingly
It is important.Wherein, ultracapacitor is a kind of novel energy storage device, and performance is between traditional capacitor and secondary cell, tool
It has the advantage that：Power density is high, is equivalent to 5-10 times of battery；Charge/discharge rates are fast, can be completed in several seconds to a few minutes,
And efficiency for charge-discharge is high；Temperature range is wide, can work in the environment of -40 ~ 70 DEG C；It has extended cycle life；It is non-maintaining, green ring
It protects.Therefore, ultracapacitor is increasingly subject to extensive concern, in consumer electronics, electric power energy, mechanical industry, new-energy automobile, life
There are huge application space and potentiality in the fields such as object sensing, space flight and aviation and military affairs.
Ultracapacitor is mainly made of four positive and negative two electrodes, collector, diaphragm and electrolyte parts, wherein influencing
The most crucial factor of ultracapacitor chemical property is exactly electrode material.Performance more preferably electrode material how is obtained, is section
The personnel of grinding do one's utmost the problem captured.To solve this problem, the Main way of ultracapacitor research and development should be found
Possess the new electrode materials of high power capacity and wide potential window.Electrode material for super capacitor is designed, should include following property：
（1）Specific surface area is big, to obtain more active sites；（2）There is the length of suitable pore-size distribution, gap network and hole
Degree, to promote ion high speed diffusion；（3）Internal conductance wants high in electrode, to provide effective charge transfer；（4）Electrochemistry
Energy and mechanical stability will be got well, to obtain good cycle performance.
In the way of energy stores, ultracapacitor can be divided into two kinds.First, double layer capacitor, electrode material master
If carbon material, in the electrolyte, charge are separated from each other, an electric double layer, the type are generated on carbon electrode/electrolyte interface
Capacitor stores charge and is realized by the electric double layer of electrode and electrolyte interface, only the accumulation of static electricity of surface charge, institute
It is relatively low with specific capacity of double-layer capacitor.Second, Faradic pseudo-capacitor, also referred to as pseudocapacitors, usually with transition metal
Object and conducting polymer are closed as electrode material, using the electrochemical redox reaction of quick electroactive material or in electrode table
The quick adsorption desorption in face stores charge, completes charge and discharge process, the specific capacitance of pseudocapacitors is higher.
Currently, the energy density of ultracapacitor is still relatively low, this is to restrict its widely applied crucial and bottleneck.
The key for improving super capacitor energy density is to improve the specific capacitance of electrode material, compared with double layer capacitor, fake capacitance
Device electrode material has notable higher specific capacitance, thus is the focus of people's research and development.Currently, people are for pseudocapacitors electrode
The research and development of material include mainly：Conducting polymer, transition metal oxide and hydroxide, transient metal sulfide etc..But this
A little materials respectively have disadvantage, and if conducting polymer cyclical stability is poor, oxide and hydroxide conductivity are low, and sulfide also has
The relatively low disadvantage of conductivity, it is even more important that the demand of high-energy density is still not achieved in the specific capacitance of above-mentioned material.Cause
And find a kind of high specific capacitance, high conductivity, high circulation stability electrode material for super capacitor become people and study and produce
The target of industry.
Transition metal selenides has high conductivity, or even has metalline, this characteristic is very beneficial for it and answers
For electrode material for super capacitor.Transition metal selenides is in fields such as catalysis, photocatalytic water, fuel sensitization solar batteries
It is applied, but then considerably less in the research of ultracapacitor and application.The exploitation of transition metal selenide material and its super
Application in grade capacitor be international forward position research and development field and high-energy density super capacitor industrialization it is important
And very potential developing direction.
Invention content
The present invention is directed to design CoNiSe2Nano-array material, and the binary selenides is synthesized using hydrothermal method,
By technical process control, make it have significant porous structure, with reach combination electrode material obtained have specific capacitance it is high,
The good goal of the invention of high rate performance, chemical property.
The present invention provides a kind of CoNiSe for ultracapacitor2Nano-array material and preparation method thereof.This hair
The bright capacitor electrode material being prepared has high specific capacitance, good high rate performance, high conductivity；Preparation manipulation letter
It is single, complex device is not needed, it can industrialized production.
Specifically, a kind of CoNiSe for ultracapacitor2Nano-array material, using nickel foam as substrate, in vertical
The nano array structure of arrangement, the nano-array is by CoNiSe2Nanometer rods and nanotube composition, the diameter of nanometer rods and nanotube
For 50 ~ 150nm, the surface of nanometer rods and nanotube is vesicular texture.
Further, the CoNiSe produced by the present invention for ultracapacitor2Nano-array material is in three-electrode system
In test, in 1 A g-1Current density under show 1338F g-1Height ratio capacity, and material resistance is down to 0.6 Ω, table
Reveal very high conductivity.
The present invention also provides prepare above-mentioned CoNiSe2The preparation method of nano-array super capacitor material, including：
（1）Nickel foam is put into hydrochloric acid solution, is ultrasonically treated, the NiO layer on surface is removed, washs to neutrality, obtains everywhere
Nickel foam after reason is CoNiSe2The growth substrate of nano-array material；
（2）Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and isopropanol are mixed, then a certain amount of glycerine is added in stirring,
Obtain precursor solution；
（3）By step（2）In obtained precursor solution pour into reaction kettle, by step（1）In treated nickel foam
It is put into reaction kettle, carries out hydro-thermal reaction, be cooled to room temperature, collect the nickel foam for being attached with product, wash, it is dry, it is steeping
The product adhered on foam nickel is CoNiSe2Presoma nanosphere；
（4）Selenium powder, sodium borohydride and water are mixed, stirs at room temperature, is configured to clear aqueous solution；
（5）By step（4）In obtained aqueous solution be transferred in reaction kettle, by step（3）In obtain have product
Nickel foam be put into reaction kettle, carry out hydro-thermal reaction, be cooled to room temperature, collect and be attached with the nickel foam of final product, washing,
It is dry, obtain the CoNiSe using nickel foam as substrate2Nano-array super capacitor material；
The step（2）Middle Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate molar ratio be 1:2~1:1, isopropanol and glycerine
It is added respectively according to the amount of every 0.125m mol Nickelous nitrate hexahydrates 40mL and 8mL.
The step（3）Middle reaction temperature is 160 ~ 200 DEG C, time 6h.
The step（4）Middle selenium powder, sodium borohydride, water ratio be 1m mol: 2m mol : 40mL.
The step（5）Middle reaction temperature is 120 ~ 180 DEG C, time 6h.
Above-mentioned each parameter is the key process parameter of the preparation method of the present invention, true through many experiments institute for inventor
Recognize, need strictly and accurately control, if exceeding the range of above-mentioned technological parameter in the experiment of inventor, can not be made
CoNiSe2Nano-array material.
The useful achievement of the present invention is：
（1）The CoNiSe for ultracapacitor that the method for the present invention is prepared2Nano-array material is Co, Ni
Binary selenides, with the corresponding binary oxide reported（CoNiO2）, binary sulfide（CoNiS2）Equal electrode materials phase
Than having higher conductivity, this characteristic to be very beneficial for transmission and transport of the electrode material to charge.
（2）The CoNiSe for ultracapacitor that the method for the present invention is prepared2Nano-array material, mainly by
CoNiSe2Nanometer rods form, and also include a small amount of CoNiSe2Nanotube, nanometer rods and nanotube surface are vesicular texture, are received
Gap between rice array is conducive to electrolyte and is permeated to electrode interior, and the porous structure of nanometer rods and nanotube surface is conducive to increase
Add electrode specific surface area, increase contact of the electrolyte with electrode material, obtain more active sites, this pattern and its aperture and
Size Distribution is advantageous to promote the high speed diffusion of ion, and obtains high chemical property.
（3）The CoNiSe for ultracapacitor that the method for the present invention is prepared2Nano-array material, not only has
High specific capacitance, while there is high conductivity and good high rate performance, electrochemical stability is good, is a kind of excellent surpass
Grade capacitor electrode material, can be applied to the ultracapacitor product of high-energy density.
（4）The method that the present invention uses hydrothermal synthesis, does not need complex device, easy to operate, is very suitable for industrializing
Batch production.
Description of the drawings
Fig. 1 is the scanning electron microscope of presoma nanosphere prepared by embodiment 1（SEM）Figure.
Fig. 2 is CoNiSe prepared by embodiment 12The scanning electron microscope of nano-array material（SEM）Figure.
Fig. 3 is CoNiSe prepared by embodiment 12The x-ray diffraction of nano-array material（XRD）Figure.
Fig. 4 is CoNiSe prepared by embodiment 12The cyclic voltammetric of nano-array material（CV）Figure.
Fig. 5 is CoNiSe prepared by embodiment 12The constant current charge-discharge curve graph of nano-array material.
Fig. 6 is CoNiSe prepared by embodiment 12Specific capacitance figure under the different current densities of nano-array material.
Fig. 7 is CoNiSe prepared by embodiment 12The ac impedance spectroscopy of nano-array material.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
（1）Nickel foam is cut into a diameter of 18mm sizes, is placed on 3 mol L-1In hydrochloric acid solution, ultrasonic reaction 30min is removed
It removes the NiO layer on surface, and treated nickel foam deionized water and ethyl alcohol is washed to neutrality.
（2）Weigh that raw material 0.125m mol Nickelous nitrate hexahydrates, that 0.125m mol cabaltous nitrate hexahydrates are dissolved in 40 mL is different
In propyl alcohol, 8mL glycerine is then added, stirs 30min, obtains precursor solution.
（3）Above-mentioned mixed solution is poured into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, it will be through（1）The nickel foam of processing is placed in it
In, reaction kettle is put into drying box, 6h is reacted under the conditions of 180 DEG C, reaction kettle is then cooled down to room temperature, collects nickel foam, point
Not Yong ethyl alcohol, deionized water rinse, and dry, the product adhered in nickel foam is CoNiSe2Presoma nanosphere.
（4）Weigh raw material 1m mol selenium powders, 2m mol sodium borohydrides are dissolved in 40mL water, at room temperature stir 10min match
It is set to clear aqueous solution and is transferred in reaction kettle.
（5）By step（3）The nickel foam with product of middle gained is put into step（4）Reaction kettle in, carry out hydro-thermal
Reaction, reaction temperature are 160 DEG C, and time 6h is cooled to room temperature, and collect nickel foam, are washed, dry, obtain be with nickel foam
The CoNiSe of substrate2Nano-array super capacitor material.
Embodiment 2
（1）Nickel foam is cut into a diameter of 18mm sizes, is so placed on 3 mol L-1In hydrochloric acid solution, ultrasonic reaction 30min,
It removes the NiO layer on surface, and treated nickel foam deionized water and ethyl alcohol is washed to neutrality.
（2）Weigh that raw material 0.125m mol Nickelous nitrate hexahydrates, that 0. 25m mol cabaltous nitrate hexahydrates are dissolved in 40 mL is different
In propyl alcohol, 8mL glycerine is then added, stirs 30min, obtains precursor solution.
（3）Above-mentioned mixed solution is poured into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, it will be through（1）The nickel foam of processing is placed in it
In, reaction kettle is put into drying box, 6h is reacted under the conditions of 180 DEG C, reaction kettle is then cooled down to room temperature, collects nickel foam, point
Not Yong ethyl alcohol, deionized water rinse, and dry, the product adhered in nickel foam is CoNiSe2Presoma nanosphere.
（4）Weigh raw material 1m mol selenium powders, 2m mol sodium borohydrides are dissolved in 40mL water, at room temperature stir 10min match
It is set to clear aqueous solution and is transferred in reaction kettle.
（5）By step（3）The nickel foam with product of middle gained is put into step（4）Reaction kettle in, carry out hydro-thermal
Reaction, reaction temperature are 160 DEG C, and time 6h is cooled to room temperature, and collect nickel foam, are washed, dry, obtain be with nickel foam
The CoNiSe of substrate2Nano-array super capacitor material.
Embodiment 3
（1）Nickel foam is cut into a diameter of 18mm sizes, is so placed on 3 mol L-1In hydrochloric acid solution, ultrasonic reaction 30min,
It removes the NiO layer on surface, and treated nickel foam deionized water and ethyl alcohol is washed to neutrality.
（2）Weigh that raw material 0.125m mol Nickelous nitrate hexahydrates, that 0.125m mol cabaltous nitrate hexahydrates are dissolved in 40 mL is different
In propyl alcohol, 8mL glycerine is then added, stirs 30min, obtains precursor solution.
（3）Above-mentioned mixed solution is poured into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, it will be through（1）The nickel foam of processing is placed in it
In, reaction kettle is put into drying box, 6h is reacted under the conditions of 160 DEG C, reaction kettle is then cooled down to room temperature, collects nickel foam, point
Not Yong ethyl alcohol, deionized water rinse, and dry, the product adhered in nickel foam is CoNiSe2Presoma nanosphere.
（4）Weigh raw material 1m mol selenium powders, 2m mol sodium borohydrides are dissolved in 40mL water, at room temperature stir 10min match
It is set to clear aqueous solution and is transferred in reaction kettle.
（5）By step（3）The nickel foam with product of middle gained is put into step（4）Reaction kettle in, carry out hydro-thermal
Reaction, reaction temperature are 180 DEG C, and time 6h is cooled to room temperature, and collect nickel foam, are washed, dry, obtain be with nickel foam
The CoNiSe of substrate2Nano-array super capacitor material.
Embodiment 4
（1）Nickel foam is cut into a diameter of 18mm sizes, is so placed on 3 mol L-1In hydrochloric acid solution, ultrasonic reaction 30min,
It removes the NiO layer on surface, and treated nickel foam deionized water and ethyl alcohol is washed to neutrality.
（2）Weigh that raw material 0.125m mol Nickelous nitrate hexahydrates, that 0.125m mol cabaltous nitrate hexahydrates are dissolved in 40 mL is different
In propyl alcohol, 8mL glycerine is then added, stirs 30min, obtains precursor solution.
（3）Above-mentioned mixed solution is poured into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, it will be through（1）The nickel foam of processing is placed in it
In, reaction kettle is put into drying box, 6h is reacted under the conditions of 200 DEG C, reaction kettle is then cooled down to room temperature, collects nickel foam, point
Not Yong ethyl alcohol, deionized water rinse, and dry, the product adhered in nickel foam is CoNiSe2Presoma nanosphere.
（4）Weigh raw material 1m mol selenium powders, 2m mol sodium borohydrides are dissolved in 40mL water, at room temperature stir 10min match
It is set to clear aqueous solution and is transferred in reaction kettle.
（5）By step（3）The nickel foam with product of middle gained is put into step（4）Reaction kettle in, carry out hydro-thermal
Reaction, reaction temperature are 120 DEG C, and time 6h is cooled to room temperature, and collect nickel foam, are washed, dry, obtain be with nickel foam
The CoNiSe of substrate2Nano-array super capacitor material.
Performance test：
1）SEM is tested：Sample prepared by above-mentioned each example is observed under a scanning electron microscope.Fig. 1 is 1 step of embodiment
Suddenly（3）In obtained CoNiSe2The microscopic appearance figure of presoma nanosphere, it can be seen that be made of uniform nanosphere, size
About 400nm；Fig. 2 is the final CoNiSe obtained of embodiment 12Microscopic appearance, there it can be seen that sample shows as nanometer
Stick also includes a small amount of nanotube, and a diameter of 50 ~ 150nm of nanometer rods and nanotube, nanometer rods and nanotube surface are porous
Shape structure, nanometer rods and nanotube are overlapping to form nano-array, and the gap between nano-array is conducive to electrolyte to electrode interior
The porous structure of infiltration, nanometer rods and nanotube surface is conducive to increase electrode specific surface area, increases electrolyte and electrode material
Contact, obtain more active sites, this pattern and its aperture and Size Distribution are advantageous to promote the high speed of ion to expand
It dissipates, and obtains high chemical property.
2）XRD is tested：Above-mentioned each example is prepared into finally obtained sample and carries out XRD tests, Fig. 3 is made for embodiment 1
CoNiSe2The XRD diagram that nano-array testing of materials obtains, X-ray diffraction peak and CoNiSe2Characteristic spectrum it is corresponding, show
Sample composition is CoNiSe2。
3）Electrochemical property test：By CoNiSe made from above-mentioned each example2Nano-array is assembled into electrode three respectively
Electrochemical property test is carried out under electrode system, Fig. 4 is CoNiSe made from embodiment 12Nano-array is in different scanning rates
Under CV curves, it can be seen that have apparent redox peaks, illustrate material have good fake capacitance characteristic；Fig. 5 is real
Apply CoNiSe made from example 12Discharge curve of the nano-array under different current densities, discharge curve have apparent platform,
Confirm CoNiSe2With fake capacitance characteristic；Fig. 6 is to calculate CoNiSe made from the embodiment 1 of gained according to Fig. 52Nano-array
Specific capacitance value under different current densities, in 1 A g-1Current density under show 1338F g-1Height ratio capacity, table
Bright CoNiSe2Nano-array material has high specific capacitance；Fig. 7 is the AC impedance figure of sample made from embodiment 1, it can be deduced that
Material resistance is 0.6 ohm, shows material satisfactory electrical conductivity.
Claims (7)
1. a kind of CoNiSe for ultracapacitor2Nano-array material, it is characterised in that：The CoNiSe2Nano-array material
Material is using nickel foam as substrate, and in the nano array structure being vertically arranged, the nano-array is by CoNiSe2Nanometer rods and nanotube
The surface of composition, a diameter of 50 ~ 150nm of nanometer rods and nanotube, nanometer rods and nanotube is vesicular texture.
2. a kind of CoNiSe for ultracapacitor according to claim 12Nano-array material, it is characterised in that：Institute
State CoNiSe2Nano-array material, in 1 A g-1Current density under reach 1338F g-1Specific capacity, material resistance down to
0.6Ω。
3. preparing the CoNiSe for ultracapacitor described in any one of claim 1 to 22The method of nano-array material,
It is characterized in that, step includes：
1）Nickel foam is put into hydrochloric acid solution, is ultrasonically treated, removes the NiO layer on surface, is washed to neutrality, obtains that treated
Nickel foam is CoNiSe2The growth substrate of nano-array material；
2）Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and isopropanol are mixed, then stirring is added a certain amount of glycerine, obtains
Precursor solution；
3）By step 2）In obtained precursor solution pour into reaction kettle, by step 1）In treated that nickel foam is put into reaction
In kettle, hydro-thermal reaction is carried out, is then cooled to room temperature, collect the nickel foam for being attached with product, washed, it is dry, in nickel foam
The product of upper attachment is CoNiSe2Presoma nanosphere；
4）Selenium powder, sodium borohydride and water are mixed, stirs at room temperature, is configured to clear aqueous solution；
5）By step 4）In obtained aqueous solution be transferred in reaction kettle, by step 3）In obtain the nickel foam for being attached with product
It is put into reaction kettle, carries out hydro-thermal reaction, then cool to room temperature, collect the nickel foam for being attached with final product, wash, do
It is dry, obtain the CoNiSe using nickel foam as substrate2Nano-array super capacitor material.
4. a kind of CoNiSe for ultracapacitor according to claim 32The preparation method of nano-array material, it is special
Sign is：The step 2）Middle Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate molar ratio be 1:2~1:1, isopropanol and glycerine divide
It is not added according to the amount of every 0.125m mol Nickelous nitrate hexahydrates 40mL and 8mL.
5. a kind of CoNiSe for ultracapacitor according to claim 32The preparation method of nano-array material, it is special
Sign is：The step 3）Middle reaction temperature is 160 ~ 200 DEG C, time 6h.
6. a kind of CoNiSe for ultracapacitor according to claim 32The preparation method of nano-array material, it is special
Sign is：The step 4）Middle selenium powder, sodium borohydride, water ratio be 1m mol: 2m mol : 40mL.
7. a kind of CoNiSe for ultracapacitor according to claim 32The preparation method of nano-array material, it is special
Sign is：The step 5）Middle reaction temperature is 120 ~ 180 DEG C, time 6h.
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