CN106098402A - 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 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 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 10
- 239000000758 substrate Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 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
- 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
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000007795 chemical reaction 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 12
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- -1 Transition metal selenides Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229950000845 politef Drugs 0.000 description 4
- 229960005335 propanol Drugs 0.000 description 4
- 239000000126 substance Substances 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
- 238000012827 research and development Methods 0.000 description 3
- 150000003346 selenoethers Chemical class 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 238000004146 energy storage 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
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229940044613 1-propanol Drugs 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
- 239000013543 active substance Substances 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 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
- 239000012466 permeate Substances 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
- 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
- 238000004154 testing of material Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Nanotechnology (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 carried out pretreatment, as the collector of electrode；In foam nickel base, first grow precursor nanosphere；Then by precursor selenizing, i.e. can get CoNiSe2Nano-array.Preparation method of the present invention is simple to operate, it is not necessary to complex device, with low cost；The CoNiSe of preparation2In nano array structure, nano-array is by CoNiSe2Nanometer rods and nanotube composition, nanometer rods and a diameter of 50 ~ 100nm of nanotube, the surface of nanometer rods and nanotube is vesicular texture.The CoNiSe that the present invention prepares2Nano-array material is at 1 A g‑1Electric current density under show 1338F g‑1Height ratio capacity, there is good high rate performance and superior electrochemical stability simultaneously, be the electrode material for super capacitor of a kind of excellence.
Description
Technical field
The present invention relates to the field of electrode material for super capacitor, particularly to a kind of transition gold for ultracapacitor
Belong to binary selenides electrode material and preparation method thereof.
Background technology
Along 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 resource, such as solar energy, wind energy, tide energy, nuclear energy, bioenergy etc..At energy
Source domain, exploitation is a kind of efficiently, low cost, long-life, eco-friendly energy conversion and storage system have seemed increasingly
Important.Wherein, ultracapacitor is a kind of novel energy storage device, and performance, between traditional capacitor and secondary cell, has
Have the advantage that: power density is high, is equivalent to 5-10 times of battery；Charge/discharge rates is fast, can complete in several seconds to a few minutes,
And efficiency for charge-discharge is high；Temperature range width, can work in the environment of-40 ~ 70 DEG C；Have extended cycle life；Non-maintaining, green ring
Protect.Therefore, ultracapacitor is increasingly subject to extensive concern, in consumer electronics, electric power energy, mechanical industry, new-energy automobile, life
All there are huge application space and potentiality in the fields such as thing sensing, space flight and aviation and military affairs.
Ultracapacitor is mainly made up of positive and negative two electrodes, collector, barrier film and four parts of electrolyte, wherein affects
The most crucial factor of ultracapacitor chemical property is exactly electrode material.How to obtain the electrode material that performance is more excellent, be section
The personnel of grinding do one's utmost the difficult problem captured.For solving this problem, the Main way of ultracapacitor research and development should be to find
Have high power capacity and the new electrode materials of wide potential window.Design electrode material for super capacitor, should include following character:
(1) specific surface area wants big, to obtain more active site；(2) there is suitable pore-size distribution, gap network, and the length in hole
Degree, to promote ion high speed diffusion；(3) in electrode, internal conductance wants height, to provide effective charge transfer；(4) electrochemistry
Energy and mechanical stability to be got well, to obtain good cycle performance.
According to the mode of energy storage, ultracapacitor can be divided into two kinds.One, double layer capacitor, electrode material master
If material with carbon element, in the electrolyte, electric charge is separated from each other, and produces an electric double layer, the type on carbon electrode/electrolyte interface
Capacitor storage electric charge relies on the electric double layer of electrode and electrolyte interface to realize, the only accumulation of static electricity of surface charge, institute
Relatively low with specific capacity of double-layer capacitor.Its two, Faradic pseudo-capacitor, also referred to as pseudocapacitors, generally with transition metal
Compound and conducting polymer, as electrode material, utilize the electrochemical redox reaction of fast electric active substance or at electrode table
The quick adsorption desorption in face stores electric charge, completes charge and discharge process, and the ratio electric capacity of pseudocapacitors is higher.
At present, the energy density of ultracapacitor is the most on the low side, and this is to restrict its wide variety of key and bottleneck.
Improve super capacitor energy density it is crucial that improve electrode material ratio electric capacity, compared with double layer capacitor, fake capacitance
Device electrode material has significantly higher ratio electric capacity, thus is the focuses researched and developed of people.At present, people are for pseudocapacitors electrode
The research and development of material specifically include that conducting polymer, transition metal oxide and hydroxide, transient metal sulfide etc..But this
A little materials are all respectively arranged with shortcoming, and as poor in conducting polymer cyclical stability, oxide and hydroxide electrical conductivity are low, and sulfide also has
The shortcoming that electrical conductivity is relatively low, it is even more important that the ratio electric capacity of above-mentioned material does not still reach the demand of high-energy-density.Cause
And, find a kind of high specific capacitance, high conductivity, the electrode material for super capacitor of high cyclical stability become people's research and produce
The target of industry.
Transition metal selenides has high electrical conductivity, even has metalline, and this characteristic is very beneficial for it should
For electrode material for super capacitor.Transition metal selenides is in fields such as catalysis, photocatalytic water, fuel sensitization solar batteries
Obtain application, but the most considerably less in research and the application of ultracapacitor.The exploitation of transition metal selenide material and super
The research and development field in the forward position, the application Shi Yige world in level capacitor, is also the important of high-energy density super capacitor industrialization
And the most potential developing direction.
Summary of the invention
It is contemplated that design CoNiSe2Nano-array material, and use hydrothermal method to synthesize this binary selenides,
Pass through technical process control so that it is there is significant loose structure, with reach prepared combination electrode material have higher than electric capacity,
The goal of the invention that high rate performance, chemical property are good.
The invention provides a kind of CoNiSe for ultracapacitor2Nano-array material and preparation method thereof.This
The bright capacitor electrode material prepared has high ratio electric capacity, good high rate performance, high electrical conductivity；Preparation manipulation letter
Single, it is not necessary to complex device, can industrialized production.
Concrete, a kind of CoNiSe for ultracapacitor2Nano-array material, with nickel foam as substrate, in vertically
The nano array structure of arrangement, this nano-array is by CoNiSe2Nanometer rods and nanotube composition, nanometer rods and the diameter of nanotube
Be the surface of 50 ~ 150nm, nanometer rods and nanotube be vesicular texture.
Further, the CoNiSe for ultracapacitor that the present invention prepares2Nano-array material is at three-electrode system
In test, at 1 A g-1Electric current density under show 1338F g-1Height ratio capacity, and material internal resistance as little as 0.6 Ω, table
Reveal the highest electrical conductivity.
Present invention also offers and prepare above-mentioned CoNiSe2The preparation method of nano-array super capacitor material, including:
(1) nickel foam is put in hydrochloric acid solution, supersound process, remove the NiO layer on surface, washing is to neutral, after being processed
Nickel foam, for CoNiSe2The growth substrate of nano-array material；
(2) Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and isopropanol are mixed, stirring, be subsequently adding a certain amount of glycerol, obtain
Precursor solution；
(3) pouring in reactor by the precursor solution obtained in step (2), the nickel foam after processing in step (1) is put into
In reactor, carry out hydro-thermal reaction, be cooled to room temperature, collect the nickel foam being attached with product, washing, be dried, in nickel foam
The product of upper attachment is CoNiSe2Presoma nanosphere；
(4) selenium powder, sodium borohydride and water are mixed, stir under room temperature, be configured to clear aqueous solution；
(5) aqueous solution obtained in step (4) is transferred in reactor, the bubble with product that will obtain in step (3)
Foam nickel is put in reactor, carries out hydro-thermal reaction, is cooled to room temperature, collects the nickel foam being attached with end product, washing, does
Dry, obtain the CoNiSe with nickel foam as substrate2Nano-array super capacitor material；
In described step (2), Nickelous nitrate hexahydrate, the mol ratio of cabaltous nitrate hexahydrate are 1:2 ~ 1:1, and isopropanol and glycerol are respectively
Add according to the amount of every 0.125m mol Nickelous nitrate hexahydrate 40mL and 8mL.
In described step (3), reaction temperature is 160 ~ 200 DEG C, and the time is 6h.
In described step (4), selenium powder, sodium borohydride, the ratio of water are 1m mol: 2m mol: 40mL.
In described step (5), reaction temperature is 120 ~ 180 DEG C, and the time is 6h.
Above-mentioned each parameter is the key process parameter of the preparation method of the present invention, for inventor through many experiments institute really
Recognize, need strict and accurately control, if beyond the scope of above-mentioned technological parameter in the experiment of inventor, then cannot prepare
CoNiSe2Nano-array material.
The useful achievement of the present invention is:
(1) CoNiSe for ultracapacitor that the method for the present invention prepares2Nano-array material, for the two of Co, Ni
Unit's selenides, with the corresponding binary oxide (CoNiO reported2), binary sulfide (CoNiS2) etc. electrode material compare,
Having higher electrical conductivity, this characteristic is very beneficial for electrode material to the transmission of electric charge and transport.
(2) CoNiSe for ultracapacitor that the method for the present invention prepares2Nano-array material, mainly by
CoNiSe2Nanometer rods forms, and also includes a small amount of CoNiSe2Nanotube, nanometer rods and nanotube surface are vesicular texture, receive
Gap between rice array is conducive to electrolyte to permeate to electrode interior, and the loose structure of nanometer rods and nanotube surface is conducive to increasing
Add electrode specific surface area, increase contacting of electrolyte and electrode material, it is thus achieved that more active site, this pattern and aperture thereof with
Distribution of sizes is advantageous to promote the high speed diffusion of ion, and obtains high chemical property.
(3) CoNiSe for ultracapacitor that the method for the present invention prepares2Nano-array material, not only has
High ratio electric capacity, has high electrical conductivity and good high rate performance simultaneously, and electrochemical stability is good, is the super of a kind of excellence
Level capacitor electrode material, can be applicable to the ultracapacitor product of high-energy-density.
(4) method that the present invention uses Hydrothermal Synthesis, it is not necessary to complex device, simple to operate, it is very suitable for industrialization
Batch production.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) figure of the presoma nanosphere of embodiment 1 preparation.
Fig. 2 is the CoNiSe of embodiment 1 preparation2Scanning electron microscope (SEM) figure of nano-array material.
Fig. 3 is the CoNiSe of embodiment 1 preparation2X-ray diffraction (XRD) figure of nano-array material.
Fig. 4 is the CoNiSe of embodiment 1 preparation2Cyclic voltammetric (CV) figure of nano-array material.
Fig. 5 is the CoNiSe of embodiment 1 preparation2The constant current charge-discharge curve chart of nano-array material.
Fig. 6 is the CoNiSe of embodiment 1 preparation2Ratio capacitance map under the different electric current densities of nano-array material.
Fig. 7 is the CoNiSe of embodiment 1 preparation2The ac impedance spectroscopy of nano-array material.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
(1) nickel foam is cut into a diameter of 18mm size, is placed on 3 mol L-1In hydrochloric acid solution, ultrasonic reaction 30min, remove
The NiO layer on surface, and nickel foam deionized water after processing and washing with alcohol are to neutral.
(2) weigh raw material 0.125m mol Nickelous nitrate hexahydrate, that 0.125m mol cabaltous nitrate hexahydrate is dissolved in 40 mL is different
In propanol, it is subsequently adding 8mL glycerol, stirs 30min, obtain precursor solution.
(3) above-mentioned mixed solution is poured in politef hydrothermal reaction kettle, the nickel foam processed through (1) is placed in it
In, reactor is put in drying baker, under the conditions of 180 DEG C, react 6h, then cooling reactor is to room temperature, collects nickel foam, point
Not Yong ethanol, deionized water rinsing, and be dried, in nickel foam, the product of attachment is CoNiSe2Presoma nanosphere.
(4) weigh raw material 1m mol selenium powder, 2m mol sodium borohydride is dissolved in 40mL water, stirs 10min and join under room temperature
It is set to clear aqueous solution and transfers in reactor.
(5) by during the nickel foam with product of gained puts into the reactor of step (4) in step (3), hydro-thermal is carried out
Reaction, reaction temperature is 160 DEG C, and the time is 6h, is cooled to room temperature, collects nickel foam, washing, is dried, obtain with nickel foam be
The CoNiSe of substrate2Nano-array super capacitor material.
Embodiment 2
(1) nickel foam is cut into a diameter of 18mm size, is so placed on 3 mol L-1In hydrochloric acid solution, ultrasonic reaction 30min, removes
Remove the NiO layer on surface, and nickel foam deionized water after processing and washing with alcohol are to neutral.
(2) weigh raw material 0.125m mol Nickelous nitrate hexahydrate, that 0. 25m mol cabaltous nitrate hexahydrate is dissolved in 40 mL is different
In propanol, it is subsequently adding 8mL glycerol, stirs 30min, obtain precursor solution.
(3) above-mentioned mixed solution is poured in politef hydrothermal reaction kettle, the nickel foam processed through (1) is placed in it
In, reactor is put in drying baker, under the conditions of 180 DEG C, react 6h, then cooling reactor is to room temperature, collects nickel foam, point
Not Yong ethanol, deionized water rinsing, and be dried, in nickel foam, the product of attachment is CoNiSe2Presoma nanosphere.
(4) weigh raw material 1m mol selenium powder, 2m mol sodium borohydride is dissolved in 40mL water, stirs 10min and join under room temperature
It is set to clear aqueous solution and transfers in reactor.
(5) by during the nickel foam with product of gained puts into the reactor of step (4) in step (3), hydro-thermal is carried out
Reaction, reaction temperature is 160 DEG C, and the time is 6h, is cooled to room temperature, collects nickel foam, washing, is dried, obtain with nickel foam be
The CoNiSe of substrate2Nano-array super capacitor material.
Embodiment 3
(1) nickel foam is cut into a diameter of 18mm size, is so placed on 3 mol L-1In hydrochloric acid solution, ultrasonic reaction 30min, removes
Remove the NiO layer on surface, and nickel foam deionized water after processing and washing with alcohol are to neutral.
(2) weigh raw material 0.125m mol Nickelous nitrate hexahydrate, that 0.125m mol cabaltous nitrate hexahydrate is dissolved in 40 mL is different
In propanol, it is subsequently adding 8mL glycerol, stirs 30min, obtain precursor solution.
(3) above-mentioned mixed solution is poured in politef hydrothermal reaction kettle, the nickel foam processed through (1) is placed in it
In, reactor is put in drying baker, under the conditions of 160 DEG C, react 6h, then cooling reactor is to room temperature, collects nickel foam, point
Not Yong ethanol, deionized water rinsing, and be dried, in nickel foam, the product of attachment is CoNiSe2Presoma nanosphere.
(4) weigh raw material 1m mol selenium powder, 2m mol sodium borohydride is dissolved in 40mL water, stirs 10min and join under room temperature
It is set to clear aqueous solution and transfers in reactor.
(5) by during the nickel foam with product of gained puts into the reactor of step (4) in step (3), hydro-thermal is carried out
Reaction, reaction temperature is 180 DEG C, and the time is 6h, is cooled to room temperature, collects nickel foam, washing, is dried, obtain with nickel foam be
The CoNiSe of substrate2Nano-array super capacitor material.
Embodiment 4
(1) nickel foam is cut into a diameter of 18mm size, is so placed on 3 mol L-1In hydrochloric acid solution, ultrasonic reaction 30min, removes
Remove the NiO layer on surface, and nickel foam deionized water after processing and washing with alcohol are to neutral.
(2) weigh raw material 0.125m mol Nickelous nitrate hexahydrate, that 0.125m mol cabaltous nitrate hexahydrate is dissolved in 40 mL is different
In propanol, it is subsequently adding 8mL glycerol, stirs 30min, obtain precursor solution.
(3) above-mentioned mixed solution is poured in politef hydrothermal reaction kettle, the nickel foam processed through (1) is placed in it
In, reactor is put in drying baker, under the conditions of 200 DEG C, react 6h, then cooling reactor is to room temperature, collects nickel foam, point
Not Yong ethanol, deionized water rinsing, and be dried, in nickel foam, the product of attachment is CoNiSe2Presoma nanosphere.
(4) weigh raw material 1m mol selenium powder, 2m mol sodium borohydride is dissolved in 40mL water, stirs 10min and join under room temperature
It is set to clear aqueous solution and transfers in reactor.
(5) by during the nickel foam with product of gained puts into the reactor of step (4) in step (3), hydro-thermal is carried out
Reaction, reaction temperature is 120 DEG C, and the time is 6h, is cooled to room temperature, collects nickel foam, washing, is dried, obtain with nickel foam be
The CoNiSe of substrate2Nano-array super capacitor material.
Performance test:
1) SEM test: sample prepared by above-mentioned each example is observed under a scanning electron microscope.Fig. 1 is embodiment 1 step
(3) CoNiSe obtained in2The microscopic appearance figure of presoma nanosphere, it can be seen that being made up of uniform nanosphere, size is big
It is about 400nm；Fig. 2 is the CoNiSe that embodiment 1 finally prepares2Microscopic appearance, there it can be seen that sample shows as nanometer
Rod, also includes that a diameter of 50 ~ 150nm of a small amount of nanotube, nanometer rods and nanotube, nanometer rods and nanotube surface are porous
Shape structure, nanometer rods and nanotube are overlapping forms nano-array, and the gap between nano-array is conducive to electrolyte to electrode interior
Infiltration, the loose structure of nanometer rods and nanotube surface is conducive to increasing electrode specific surface area, increases electrolyte and electrode material
Contact, it is thus achieved that more active site, this pattern and aperture and distribution of sizes thereof are advantageous to promote that the high speed of ion expands
Dissipate, and obtain high chemical property.
2) XRD test: the sample that the preparation of above-mentioned each example finally gives is carried out XRD test, Fig. 3 is that embodiment 1 prepares
CoNiSe2The XRD figure that nano-array testing of materials obtains, X-ray diffraction peak and CoNiSe2Characteristic spectrum corresponding, show
Sample composition is CoNiSe2。
3) electrochemical property test: the CoNiSe that above-mentioned each example is prepared2Nano-array is assembled into electrode respectively three
Carrying out electrochemical property test under electrode system, Fig. 4 is the CoNiSe that embodiment 1 prepares2Nano-array is at different scanning rates
Under CV curve, it can be seen that having obvious oxidoreduction peak, illustrative material has good fake capacitance characteristic；Fig. 5 is real
Execute the CoNiSe that example 1 prepares2Nano-array discharge curve under different electric current densities, discharge curve has obvious platform,
Confirm CoNiSe2There is fake capacitance characteristic；Fig. 6 is to calculate, according to Fig. 5, the CoNiSe that the embodiment 1 of gained prepares2Nano-array
Ratio capacitance under different electric current densities, at 1 A g-1Electric current 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 the sample that embodiment 1 prepares, it can be deduced that
Material internal resistance is 0.6 ohm, shows material satisfactory electrical conductivity.
Claims (7)
1. the CoNiSe for ultracapacitor2Nano-array material, it is characterised in that: described CoNiSe2Nano-array material
Material is with nickel foam as substrate, and in the nano array structure being vertically arranged, described nano-array is by CoNiSe2Nanometer rods and nanotube
Composition, nanometer rods and a diameter of 50 ~ 150nm of nanotube, the surface of nanometer rods and nanotube is vesicular texture.
A kind of CoNiSe for ultracapacitor the most according to claim 12Nano-array material, it is characterised in that: institute
State CoNiSe2Nano-array material, at 1 A g-1Electric current density be issued to 1338F g-1Specific capacity, material internal resistance is as little as
0.6Ω。
3. the preparation CoNiSe for ultracapacitor according to any one of claim 1 to 22The method of nano-array material,
It is characterized in that, step includes:
1) nickel foam is put in hydrochloric acid solution, supersound process, remove the NiO layer on surface, washing is to neutral, after being processed
Nickel foam, for CoNiSe2The growth substrate of nano-array material；
2) Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and isopropanol are mixed, stirring, be subsequently adding a certain amount of glycerol, obtain
Precursor solution；
3) by step 2) in the precursor solution that obtains pour in reactor, the nickel foam after processing in step 1) puts into reaction
In still, carry out hydro-thermal reaction, be then cooled to room temperature, collect the nickel foam being attached with product, washing, be dried, in nickel foam
The product of upper attachment is CoNiSe2Presoma nanosphere；
4) selenium powder, sodium borohydride and water are mixed, stir under room temperature, be configured to clear aqueous solution；
5) aqueous solution obtained in step 4) is transferred in reactor, step 3) will obtain being attached with the nickel foam of product
Put in reactor, carry out hydro-thermal reaction, be then cooled to room temperature, collect the nickel foam being attached with end product, washing, do
Dry, obtain the CoNiSe with nickel foam as substrate2Nano-array super capacitor material.
A kind of CoNiSe for ultracapacitor2The preparation method of nano-array material, it is special
Levy and be: described step 2) in Nickelous nitrate hexahydrate, the mol ratio of cabaltous nitrate hexahydrate be that 1:2 ~ 1:1, isopropanol and glycerol divide
Do not add according to the amount of every 0.125m mol Nickelous nitrate hexahydrate 40mL and 8mL.
A kind of CoNiSe for ultracapacitor2The preparation method of nano-array material, it is special
Levying and be: in described step 3), reaction temperature is 160 ~ 200 DEG C, the time is 6h.
A kind of CoNiSe for ultracapacitor2The preparation method of nano-array material, it is special
Levy and be: in described step 4), selenium powder, sodium borohydride, the ratio of water are 1m mol: 2m mol: 40mL.
A kind of CoNiSe for ultracapacitor2The preparation method of nano-array material, it is special
Levying and be: in described step 5), reaction temperature is 120 ~ 180 DEG C, the time is 6h.
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| CN108735522A (en) * | 2018-05-25 | 2018-11-02 | 西南大学 | A kind of CoNiO2/ MXene composite material and preparation methods and application |
| CN109003824A (en) * | 2018-06-29 | 2018-12-14 | 安阳师范学院 | Ternary cobalt nickel selenides nano-chip arrays electrode material and preparation method thereof |
| CN109346330A (en) * | 2018-09-11 | 2019-02-15 | 湖北大学 | Flexible cotton supported bi-metallic selenides NixCo9-xSe electrode material for super capacitor and its preparation method and application |
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| CN107311119A (en) * | 2017-06-27 | 2017-11-03 | 武汉理工大学 | Hollow nanoprisms material of the cobalt nickel of four selenizing two and its preparation method and application |
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| CN109003824A (en) * | 2018-06-29 | 2018-12-14 | 安阳师范学院 | Ternary cobalt nickel selenides nano-chip arrays electrode material and preparation method thereof |
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| CN109524245B (en) * | 2018-11-20 | 2020-09-18 | 东南大学 | Preparation method of high-performance nickel-cobalt selenide/three-dimensional graphene/foamed nickel binder-free electrode material |
| CN110614105A (en) * | 2019-09-25 | 2019-12-27 | 上海应用技术大学 | Mo for hydrogen evolution2C/NiCoSex heterojunction electrocatalytic material and preparation method thereof |
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