CN110233056A - A kind of Co-Ni-S nanometer sheet material and the preparation method and application thereof - Google Patents
A kind of Co-Ni-S nanometer sheet material and the preparation method and application thereof Download PDFInfo
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- CN110233056A CN110233056A CN201910517921.8A CN201910517921A CN110233056A CN 110233056 A CN110233056 A CN 110233056A CN 201910517921 A CN201910517921 A CN 201910517921A CN 110233056 A CN110233056 A CN 110233056A
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- 239000000463 material Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 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
- 238000005119 centrifugation Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- -1 polytetrafluoroethylene Polymers 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000006229 carbon black Substances 0.000 claims description 13
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- 239000006260 foam Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 229910002441 CoNi Inorganic materials 0.000 abstract description 21
- 239000002904 solvent Substances 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 239000002305 electric material Substances 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000008267 milk Substances 0.000 description 3
- 210000004080 milk Anatomy 0.000 description 3
- 235000013336 milk Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 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 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, 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
- H01G11/84—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)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Nanotechnology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention relates to a kind of Co-Ni-S nanometer sheet material and the preparation method and application thereof, the preparation method of nanometer sheet material the following steps are included: 1) by soluble nickel salt, soluble cobalt and urea it is soluble in water after, thiocarbamide is added and simultaneously carries out hydro-thermal reaction；2) after reaction, through centrifugation, washing, dry to get arriving CoNi2S4Nanometer sheet material；Nanometer sheet material is prepared into working electrode, in supercapacitor.Compared with prior art, CoNi of the present invention2S4The preparation method of nanometer sheet material is environmental-friendly, simple and convenient, has synthesized CoNi using a step solvent thermal reaction2S4Nanometer sheet material, enormously simplifies reaction step, shortens generated time, improves reaction rate and efficiency, convenient for the CoNi of high-purity is mass produced2S4Nanometer sheet；And CoNi2S4Nanometer sheet material has high-specific surface area, very high specific capacitance, good cycle performance and high-energy density, and electrochemical performance can be further prepared into working electrode, in supercapacitor.
Description
Technical field
The invention belongs to electrochemistry and technical field of nano material, it is related to a kind of Co-Ni-S nanometer sheet material and its preparation
Method and the application in supercapacitor.
Background technique
Exhaustion with fossil energy and the environmental problem that continuously emerges, the exploitation of renewable and clean energy resource, using becoming
It is more and more important.Solar energy, wind energy are most abundant most important renewable and clean energy resources, but changeable due to solar energy and wind energy
Unstable natural characteristic causes the power generation of solar energy and wind energy output also to show intermittent, changeable feature.In order to make this
A little energy products can incorporate power grid, and energy-storage system and new energy product are used cooperatively to construct smart grid just and become especially
It is important.Application study with high power density, the energy storage device of high-energy density, which will construct advanced energy-storage system to future, to be had
It is significant.
Supercapacitor have superelevation power density, be characteristic not available for other all energy storage devices and its
Core competitiveness.Transient metal sulfide have low electronegativity and high electrochemical performance, increasingly attract vast researcher into
Row research.Wherein, bimetallic sulfide is all apparently higher than oxide/hydroxide because of its electro-chemical activity and conductivity, by
Research extensively.Since nickel sulfide and cobalt sulfide have multivalent state, so they can effectively be integrated, and have very much
Redox active site, to increase electro-chemical activity and electric conductivity.Although binary nickel sulfide or cobalt sulfide can be formed
Different crystal structures, but there are still limitations.
Zhu Zhaoqiang preparation in " the nanocrystalline preparation of ternary cobalt nickel sulfide and its application in supercapacitor field "
A kind of CoNi is gone out2S4Nanoparticle, preparation process are as follows: cobalt acetate, nickel acetate are set in a round bottom flask, sequentially added
Methyl phenyl ethers anisole, oleyl amine, then agitating and heating 30 minutes in 60 DEG C of oil bath pan.The reaction kettle for filling sulphur powder is poured into after being completely dissolved
It is put into baking oven and reacts 24 hours in liner, after sealing for 200 DEG C, cooling after taking-up, washing, centrifuge separation, drying are to get arriving
CoNi2S4Black powder.In this article, CoNi2S4Nanoparticle temperature required when preparing is higher, and the reaction time is longer, this
Outside, sulphur source used in the preparation process is sulphur powder, and sulphur powder is inflammable solid, increases the risk of material preparation process.
And in the present invention, ternary vulcanizes nickel cobalt (CoNi2S4) nanometer sheet material preparation process environmental protection without danger, and the material prepared
Expect that chemical property is more excellent.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of Co-Ni-S nanometer sheets
Material and the preparation method and application thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of Co-Ni-S nanometer sheet material, method includes the following steps:
1) by soluble nickel salt, soluble cobalt and urea it is soluble in water after, be added thiocarbamide simultaneously carry out hydro-thermal reaction；
2) after reaction, through centrifugation, washing, dry to get arriving CoNi2S4Nanometer sheet material.
Further, the soluble nickel salt is nickel nitrate, and the soluble cobalt is cobalt nitrate.
Further, in the hydrothermal reaction process, temperature is 160-200 DEG C, time 8-12h.
Further, the molar ratio of the soluble nickel salt, soluble cobalt and urea is 2:(0.8-1.2): (4-
6)。
Further, in step 1), after thiocarbamide is added, immediately by mixed liquor be transferred in polytetrafluoroethylene (PTFE) water heating kettle into
Row hydro-thermal reaction.
A kind of Co-Ni-S nanometer sheet material, the nanometer sheet material are prepared using the method.
The nanometer sheet material is prepared into working electrode by a kind of application of Co-Ni-S nanometer sheet material, for super
In capacitor.
Further, the preparation process of the working electrode are as follows: after nanometer sheet material is dry, grinding, with carbon black and
Polytetrafluoroethylene (PTFE) is uniformly mixed, and is pressed together on nickel foam on piece later, obtains the working electrode after drying.
Further, the mass ratio of the nanometer sheet material, carbon black and polytetrafluoroethylene (PTFE) is 8:(0.8-1.2):
(0.8-1.2)。
Further, in the drying process, temperature is 50-70 DEG C, time 10-15h.
Compared with prior art, the invention has the characteristics that:
1) the ternary vulcanization nickel cobalt (CoNi that the present invention prepares2S4) in nanometer sheet material, the overlapped formation of nano material
The flower-shaped nanostructure of the pinecone, increases the specific surface area of material, improves the rate transmitted between ion, and nanometer sheet material
Preparation method is environmental-friendly, simple and convenient, has synthesized CoNi using a step solvent thermal reaction2S4Nanometer sheet material, greatly simplifies
Reaction step, shortens generated time, improves reaction rate and efficiency, convenient for the CoNi of high-purity is mass produced2S4It receives
Rice piece；
2) CoNi that the present invention prepares2S4Nanometer sheet material has high-specific surface area, very high specific capacitance, good follows
Ring performance and high-energy density, electrochemical performance can be further prepared into working electrode, in supercapacitor.
Detailed description of the invention
Fig. 1 is CoNi obtained in embodiment 22S4SEM figure of the nanometer sheet material under 5 μm；
Fig. 2 is CoNi obtained in embodiment 22S4TEM figure of the nanometer sheet material at 100nm；
Fig. 3 is CoNi obtained in embodiment 22S4The CV of nanometer sheet material schemes；
Fig. 4 is CoNi obtained in embodiment 22S4The GCD of nanometer sheet material schemes.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention
Premised on implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to
Following embodiments.
Agents useful for same and instrument are as follows in embodiment:
Reagent: nickel nitrate hexahydrate, Cobalt(II) nitrate hexahydrate, urea, thiocarbamide, deionized water, ethyl alcohol.
Instrument: CHI760e electrochemical workstation, electronic balance, ultrasonic cleaner, Ag/AgCl electrode, platinum electrode.
Embodiment 1:
A kind of CoNi2S4The preparation step of nanometer sheet material is as follows: 0.4mmol Ni (NO)3·6H2O、0.2mmol Co
(NO3)2·6H2O and 1mmol CH4N2O is dissolved in 10mL deionized water, is vigorously stirred to solution and the face of glycan milk is presented
Color.Then it is ultrasonically treated 30min.Then, 2mmol thiocarbamide is added thereto and is quickly transferred to 40mL polytetrafluoroethyllining lining not
Solvent thermal reaction is carried out in rust steel autoclave, is maintained at 10h at 180 DEG C.Cooled down to the end of reacting, centrifugation, with deionized water and
Ethyl alcohol is cleaned multiple times, the CoNi that will be obtained2S4Nanometer sheet material is fully ground, and carbon black, polytetrafluoroethylene (PTFE) in mass ratio 8:
1:1 mixing, stirs evenly, is pressed together on foam nickel sheet (1cm × 1cm), and working electrode is made in 60 DEG C of baking 12h.
In preparation CoNi2S4During nanometer sheet material, for thiocarbamide as sulphur source, main preparating mechanism is as follows:
The method for using cyclic voltammetry and constant current charge-discharge through occasion China CHI760e electrochemical workstation, detects the material
Specific capacitance and stable circulation performance.Cyclic voltammetry test shows that material has excellent redox ability.Utilize electricity
Sub- flying-spot microscope (surface microstructure for characterizing the electrode material), the high-specific surface area for super electric material provides the foundation.
In 2mol/L KOH solution and under the current density of 0.5A/g, the specific capacitance of the electrode material has reached 1810F/g.
Embodiment 2:
A kind of CoNi2S4The preparation step of nanometer sheet material is as follows: 0.4mmol Ni (NO)3·6H2O、0.2mmol Co
(NO3)2·6H2O and 1mmol CH4N2O is dissolved in 10mL deionized water, is vigorously stirred to solution and the face of glycan milk is presented
Color.Then it is ultrasonically treated 30min.Then, 4mmol thiocarbamide is added thereto and is quickly transferred to 40mL polytetrafluoroethyllining lining not
Solvent thermal reaction is carried out in rust steel autoclave, is maintained at 10h at 180 DEG C.Cooled down to the end of reacting, centrifugation, with deionized water and
Ethyl alcohol is cleaned multiple times, the CoNi that will be obtained2S4Nanometer sheet material is fully ground, and carbon black, polytetrafluoroethylene (PTFE) in mass ratio 8:
1:1 mixing, stirs evenly, is pressed together on foam nickel sheet (1cm × 1cm), and working electrode is made in 60 DEG C of baking 12h.
The method for using cyclic voltammetry and constant current charge-discharge through occasion China CHI760e electrochemical workstation, detects the material
Specific capacitance and stable circulation performance.Cyclic voltammetry test shows that material has excellent redox ability.Utilize electricity
Sub- flying-spot microscope (surface microstructure for characterizing the electrode material), the high-specific surface area for super electric material provides the foundation.
In 2mol/L KOH solution and under the current density of 0.5A/g, the specific capacitance of the electrode material has reached 2078F/g.
Fig. 1 is CoNi obtained2S4SEM figure of the nanometer sheet material under 5 μm, as seen from Figure 1, CoNi2S4Nanometer
Material is overlapped mutually and forms multiple gaps.
Fig. 2 is CoNi obtained2S4TEM figure of the nanometer sheet material at 100nm, with hom ology CoNi2S4
The crystallization process of nano material, and its pattern is observed.As can be seen from Figure 2 nanometer crystal block is mutual overlapping, with
SEM result is consistent.
Fig. 3 is CoNi obtained2S4The CV of nanometer sheet material schemes, and sweep speed is 5~50mV s-1.It can from Fig. 3
To find out, there are symmetrical redox peaks within the scope of voltage 0-0.6V.With the increase of sweep speed, oxidation peak and reduction
It moves from right to left respectively at peak.It is worth noting that, chain image does not change, but peak position is changed.It is above-mentioned
Phenomenon shows CoNi obtained2S4Nanometer sheet material has good invertibity and stability.
Fig. 4 is CoNi obtained2S4The GCD of nanometer sheet material schemes, and in order to further study capacitive property, Fig. 4 is given
The CoNi under different current densities2S4GCD in 0~0.39V voltage range.Charging and discharging curve shows typical faraday's electricity
The characteristic in pond.Curve shows a pair of ladder platform being distributed symmetrically, and fits like a glove with the redox peaks of CV curve.In addition,
With the increase of current density, the charge and discharge time of each electrode material is reduced rapidly, but discharge voltage still keeps good with the time
Good linear relationship, illustrates CoNi2S4With good heavy-current discharge characteristic.Specific capacitance is calculated according to formula (1), works as electricity
Current density is 0.5Ag-1、1A·g-1、2A·g-1、 5A·g-1、10A·g-1When, CSSpecific capacitance value be respectively 2078Fg-1、1765F·g-1、1632F·g-1、1543F·g-1、 1341F·g-1。
Embodiment 3:
A kind of CoNi2S4The preparation step of nanometer sheet material is as follows: 0.4mmol Ni (NO)3·6H2O、0.2mmol Co
(NO3)2·6H2O and 1mmol CH4N2O is dissolved in 10mL deionized water, is vigorously stirred to solution and the face of glycan milk is presented
Color.Then it is ultrasonically treated 30min.Then, 6mmol thiocarbamide is added thereto and is quickly transferred to 40mL polytetrafluoroethyllining lining not
Solvent thermal reaction is carried out in rust steel autoclave, is maintained at 10h at 180 DEG C.Cooled down to the end of reacting, centrifugation, with deionized water and
Ethyl alcohol is cleaned multiple times, the CoNi that will be obtained2S4Nanometer sheet material is fully ground, and carbon black, polytetrafluoroethylene (PTFE) in mass ratio 8:
1:1 mixing, stirs evenly, is pressed together on foam nickel sheet (1cm × 1cm), and working electrode is made in 60 DEG C of baking 12h.
The method for using cyclic voltammetry and constant current charge-discharge through occasion China CHI760e electrochemical workstation, detects the material
Specific capacitance and cyclical stability performance.Cyclic voltammetry test shows that material has excellent redox ability.Benefit
With electronic scanner microscope (surface microstructure for characterizing the electrode material), the high-specific surface area for super electric material provides base
Plinth.In 2mol/L KOH solution and under the current density of 0.5A/g, the specific capacitance of the electrode material has reached 1562F/
g。
Embodiment 4:
A kind of Co-Ni-S nanometer sheet material, preparation method includes the following steps:
1) by nickel nitrate, cobalt nitrate and urea it is soluble in water after, be added thiocarbamide after, mixed liquor is transferred to polytetrafluoro immediately
In ethylene water heating kettle, and hydro-thermal reaction 12h is carried out at 160 DEG C, wherein the molar ratio of nickel nitrate, cobalt nitrate and urea is 2:
0.8:6；
2) after reaction, through centrifugation, washing, dry to get arriving CoNi2S4Nanometer sheet material.
The nanometer sheet material is prepared into working electrode, in supercapacitor.The preparation process of working electrode are as follows: will
After the drying of nanometer sheet material, grinding, it is uniformly mixed with carbon black and polytetrafluoroethylene (PTFE), is pressed together on nickel foam on piece later, at 50 DEG C
Working electrode is obtained after lower dry 15h.Wherein, the mass ratio of nanometer sheet material, carbon black and polytetrafluoroethylene (PTFE) is 8:0.8:
1.2。
Embodiment 5:
A kind of Co-Ni-S nanometer sheet material, preparation method includes the following steps:
1) by nickel nitrate, cobalt nitrate and urea it is soluble in water after, be added thiocarbamide after, mixed liquor is transferred to polytetrafluoro immediately
In ethylene water heating kettle, and hydro-thermal reaction 8h is carried out at 200 DEG C, wherein the molar ratio of nickel nitrate, cobalt nitrate and urea is 2:
1.2:4；
2) after reaction, through centrifugation, washing, dry to get arriving CoNi2S4Nanometer sheet material.
The nanometer sheet material is prepared into working electrode, in supercapacitor.The preparation process of working electrode are as follows: will
After the drying of nanometer sheet material, grinding, it is uniformly mixed with carbon black and polytetrafluoroethylene (PTFE), is pressed together on nickel foam on piece later, at 70 DEG C
Working electrode is obtained after lower dry 10h.Wherein, the mass ratio of nanometer sheet material, carbon black and polytetrafluoroethylene (PTFE) is 8:1.2:
0.8。
Embodiment 6:
A kind of Co-Ni-S nanometer sheet material, preparation method includes the following steps:
1) by nickel nitrate, cobalt nitrate and urea it is soluble in water after, be added thiocarbamide after, mixed liquor is transferred to polytetrafluoro immediately
In ethylene water heating kettle, and hydro-thermal reaction 10h is carried out at 180 DEG C, wherein the molar ratio of nickel nitrate, cobalt nitrate and urea is 2:
1:5；
2) after reaction, through centrifugation, washing, dry to get arriving CoNi2S4Nanometer sheet material.
The nanometer sheet material is prepared into working electrode, in supercapacitor.The preparation process of working electrode are as follows: will
After the drying of nanometer sheet material, grinding, it is uniformly mixed with carbon black and polytetrafluoroethylene (PTFE), is pressed together on nickel foam on piece later, at 60 DEG C
Working electrode is obtained after lower dry 12h.Wherein, the mass ratio of nanometer sheet material, carbon black and polytetrafluoroethylene (PTFE) is 8:1:1.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of preparation method of Co-Ni-S nanometer sheet material, which is characterized in that method includes the following steps:
1) by soluble nickel salt, soluble cobalt and urea it is soluble in water after, be added thiocarbamide simultaneously carry out hydro-thermal reaction；
2) after reaction, through centrifugation, washing, dry to get arriving CoNi2S4Nanometer sheet material.
2. a kind of preparation method of Co-Ni-S nanometer sheet material according to claim 1, which is characterized in that described can
Insoluble nickel salt is nickel nitrate, and the soluble cobalt is cobalt nitrate.
3. a kind of preparation method of Co-Ni-S nanometer sheet material according to claim 1, which is characterized in that the water
In thermal process reactor, temperature is 160-200 DEG C, time 8-12h.
4. a kind of preparation method of Co-Ni-S nanometer sheet material according to claim 1, which is characterized in that described can
The molar ratio of insoluble nickel salt, soluble cobalt and urea is 2:(0.8-1.2): (4-6).
5. a kind of preparation method of Co-Ni-S nanometer sheet material according to claim 1, which is characterized in that in step 1),
After thiocarbamide is added, mixed liquor is transferred in polytetrafluoroethylene (PTFE) water heating kettle carries out hydro-thermal reaction immediately.
6. a kind of Co-Ni-S nanometer sheet material, which is characterized in that the nanometer sheet material is used such as any one of claim 1 to 5 institute
The method stated is prepared.
7. a kind of application of Co-Ni-S nanometer sheet material as claimed in claim 6, which is characterized in that by the nanometer sheet
Material is prepared into working electrode, in supercapacitor.
8. a kind of application of Co-Ni-S nanometer sheet material according to claim 7, which is characterized in that the work electricity
The preparation process of pole are as follows: after nanometer sheet material is dry, grinding, be uniformly mixed with carbon black and polytetrafluoroethylene (PTFE), be pressed together on later
Nickel foam on piece obtains the working electrode after drying.
9. a kind of application of Co-Ni-S nanometer sheet material according to claim 8, which is characterized in that the nanometer sheet
The mass ratio of material, carbon black and polytetrafluoroethylene (PTFE) is 8:(0.8-1.2): (0.8-1.2).
10. a kind of application of Co-Ni-S nanometer sheet material according to claim 8, which is characterized in that described is dried
Cheng Zhong, temperature are 50-70 DEG C, time 10-15h.
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| CN115180660A (en) * | 2022-07-07 | 2022-10-14 | 湖北理工学院 | Synthetic method of bimetallic sulfide electrode material with flower-like hierarchical nanostructure |
| CN115180660B (en) * | 2022-07-07 | 2023-11-17 | 湖北理工学院 | Synthesis method of flower-shaped hierarchical nano-structure bimetallic sulfide electrode material |
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