CN110211812A - A kind of MnS@CoMn-LDH composite material and preparation method and application - Google Patents
A kind of MnS@CoMn-LDH composite material and preparation method and application Download PDFInfo
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- CN110211812A CN110211812A CN201910517909.7A CN201910517909A CN110211812A CN 110211812 A CN110211812 A CN 110211812A CN 201910517909 A CN201910517909 A CN 201910517909A CN 110211812 A CN110211812 A CN 110211812A
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- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004202 carbamide Substances 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 13
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005119 centrifugation Methods 0.000 claims abstract description 10
- 150000002696 manganese Chemical class 0.000 claims abstract description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 24
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 17
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical group Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 17
- 239000006260 foam Substances 0.000 claims description 17
- 239000011565 manganese chloride Substances 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 239000006229 carbon black Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 235000002867 manganese chloride Nutrition 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 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
- 230000008569 process Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 20
- 238000002484 cyclic voltammetry Methods 0.000 description 13
- 238000013019 agitation Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 239000011149 active material Substances 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- 229910006275 γ-MnS Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction 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
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical group [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of MnS@CoMn-LDH composite material and preparation methods and application, sulfide is added, and carry out a hydro-thermal reaction the following steps are included: 1) that soluble manganese salt is soluble in water in the preparation method of composite material later, by centrifugation, washing, drying, MnS is obtained；2) soluble manganese salt, soluble cobalt, ammonium fluoride and urea is soluble in water, MnS is added later, and carry out secondary water thermal response, arrives MnS CoMn-LDH composite material by cooling, centrifugation, washing, drying；Composite material is prepared into working electrode, in supercapacitor.Compared with prior art, the present invention passes through two-step hydrothermal route MnS@CoMn-LDH composite material, composite material mesoporous rich in and micropore, to reach good chemical property, and composite material and preparation method thereof is simple, it is environmental-friendly, generated time is substantially reduced, convenient for the MnS@CoMn-LDH composite material of high-purity is mass produced.
Description
Technical field
The invention belongs to electrochemistry and technical field of nano material, it is related to a kind of MnS@CoMn-LDH composite material and its system
Preparation Method and the application in supercapacitor.
Background technique
With getting worse for environmental pollution and Fossil fuel consumption, exploitation renewable energy storage equipment becomes increasingly
It is important.Supercapacitor is also known as electrochemical capacitor, because its power density is high, rate capacity is strong, charge and discharge process is fast, the circulation longevity
The advantages that ordering long (> 10 ten thousand times) and the extensive concern by industry and academia.The performance of supercapacitor substantially depends on
In the performance of electrode material.In recent years, transition metal oxide, sulfide and hydroxide are due to its higher theoretical specific capacitance
As cell type electrode material for super capacitor, and extensive research is obtained.In numerous class battery materials, transition gold
Belong to sulfide to have received widespread attention as efficient HSC electrode material, this is primarily due to and corresponding metal oxide
It compares, the band gap of transient metal sulfide is smaller, and chemical property is more superior, and conductivity is higher.
In recent years, CoS2、CuS、Ni3S2、CoNi2S4、MoS2、FeS2Equal transient metal sulfides have been widely studied,
And it can be used as the reliable electrode material of supercapacitor applications.It its electric conductivity with higher and more better than metal oxide follows
Ring performance.In various metal sulfides, MnS is a kind of p-type semiconductor that band gap is 3.1-3.7eV, it is than corresponding metal
Oxide or metal hydroxides have higher conductivity.MnS can show three polymorphs: α, β, γ-MnS.?
In these three polymorphs, green α-MnS is in rock salt structure, has stability more better than other two polymorphs；It is pink
β-MnS and the γ-MnS of color are in zincblende and wurtzite structure respectively, are metastable state.
Transition metal stratiform dihydroxyl compound (LDH) has special layer structure as a kind of two-dimentional (2D) material.
Its high surface area and quick ion-transfer rate promote their applications in energy is converted and stored.However, LDH's is poly-
Collection property and low conductivity limit ion/electronics and transport, and cause chemical property undesirable, limit it and further apply.
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 MnS@CoMn-LDH
Composite material and preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of MnS@CoMn-LDH composite material, method includes the following steps:
1) soluble manganese salt is soluble in water, sulfide is added later, and carry out a hydro-thermal reaction, by being centrifuged, wash
It washs, dry, obtain MnS；
2) soluble manganese salt, soluble cobalt, ammonium fluoride and urea is soluble in water, MnS is added later, and carry out secondary
Hydro-thermal reaction arrives the MnS@CoMn-LDH composite material by cooling, centrifugation, washing, drying.
Further, the soluble manganese salt is manganous chloride, and the sulfide is vulcanized sodium, the solubility
Cobalt salt is cobalt nitrate.
Further, in step 1), in a hydrothermal reaction process, temperature is 120-180 DEG C, time 8-
16h；In step 2), in the secondary hydrothermal reaction process, temperature is 120-180 DEG C, time 6-12h.
Further, the drying is vacuum drying, and in the drying process, and temperature is 55-65 DEG C, the time
For 10-14h.
Further, in step 2), the soluble manganese salt, soluble cobalt, the molar ratio of ammonium fluoride and urea are
1:(1.8-2.2):(4-6):(4-6)。
A kind of MnS@CoMn-LDH composite material, the composite material are prepared using the method.
A kind of application of MnS@CoMn-LDH composite material, is prepared into working electrode for the composite material, for surpassing
In grade capacitor.
Further, the preparation process of the working electrode are as follows: after grinding composite material, with carbon black and polytetrafluoroethyl-ne
Alkene 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 composite 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.
During preparing MnS@CoMn-LDH composite material, the hydrolysis of urea makes the present invention in water-heat process
Mn2+And Co2+With OH-It reacts, generates CoMn-LDH nanostructure；And the fluorine ion in ammonium fluoride selective can be adsorbed in
On crystal face, to change the crystallization kinetics behavior of each crystal face, eventually leads to crystal and generate difference on pattern, and low concentration
NH4 +It can inhibit OH-Ionization, the growth rate of CoMn-LDH reduces, and crystal can grow along specific crystal lattice orientation, formation
CoMn-LDH nanoneedle.
Compared with prior art, the invention has the characteristics that:
1) present invention is by two-step hydrothermal route MnS@CoMn-LDH composite material, during the composite material is rich in
Hole and micropore, to reach good chemical property, and composite material and preparation method thereof is simple, environmental-friendly, substantially reduces conjunction
At the time, convenient for the MnS@CoMn-LDH composite material of high-purity is mass produced；
2) present invention has unique core-shell structure, thin LDH nanometer thin by the composite material that hydro-thermal reaction is prepared
Shell material of the piece as one-dimensional nucleocapsid structure has biggish surface area, and is capable of providing electrolyte diffusion channel abundant,
The synergistic effect that thus can use two kinds of components, provides enough electroactive sites and electrolyte diffusion channel abundant；
3) there is high current density using the working electrode that the MnS@CoMn-LDH composite material in the present invention is prepared, uses
In supercapacitor, is conducive to electronics and quickly transmits.
Detailed description of the invention
Fig. 1 is the preparation route figure of MnS@CoMn-LDH composite material；
Fig. 2 sweeps the cyclic voltammograms under speed in difference for MnS@CoMn-LDH composite material obtained in embodiment 1；
Fig. 3 schemes for GCD of the MnS@CoMn-LDH composite material obtained in embodiment 1 under the current density of 1A/g；
Fig. 4 schemes for GCD of the MnS@CoMn-LDH composite material obtained in embodiment 2 under the current density of 1A/g.
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.
Various raw materials used in each embodiment are unless otherwise specified commercially available.
Embodiment 1:
A kind of preparation method of MnS CoMn-LDH composite material is as shown in Figure 1, comprising the following steps:
First step hydro-thermal, by 0.1g MnCl2·4H2O is dissolved in 25mL deionized water, is vigorously stirred lower addition 5mL
0.1mol/L Na2It after S, magnetic agitation 20min, is transferred in 50mL polytetrafluoroethyllining lining stainless steel autoclave, carries out first
Hydro-thermal reaction is walked, hydrothermal temperature is 120 DEG C, the hydro-thermal reaction time 8h；By after hydro-thermal sample take out cooling, then from
The heart, washing, 60 DEG C of vacuum drying 12h, obtain MnS powder.Second step hydro-thermal, by 1mmolMnCl2·4H2O、2mmol Co
(NO3)2·6H2O、5mmolNH4F, 5mmol urea is dissolved in deionized water, and after magnetic agitation 30min, first step water is added
MnS sample made from heat is transferred in polytetrafluoroethyllining lining stainless steel autoclave after mixing to it, carries out second step water
Thermal response, hydrothermal temperature are 120 DEG C, the hydro-thermal reaction time 6h；Sample after hydro-thermal is taken out into cooling, be then centrifuged for,
Washing, 60 DEG C of vacuum drying 12h, obtain MnS@CoMn-LDH powder.After the active material is ground, with carbon black, polytetrafluoro
Ethylene 8:1:1 in mass ratio is uniformly mixed, and is pressed together on foam nickel sheet (1cm × 1cm), and dry 12h, obtains in 60 DEG C of baking oven
MnS@CoMn-LDH working electrode (note MSCM-1).
The method for using cyclic voltammetry and constant current charge-discharge through occasion China CHI760e electrochemical workstation, using three electrodes
System: using the foam nickel sheet of MSCM-1 as working electrode, using Ag/AgCl electrode as reference electrode, with Pt electrode be to electrode, with
2mol/L KOH is electrolyte solution.Detect the specific capacitance and stable circulation performance of the composite material, cyclic voltammetry test knot
Fruit is as shown in Fig. 2, show that the composite material has excellent redox ability.Fig. 3 is that the GCD of composite material schemes, and can be seen
Out, in 2mol/L KOH solution and under the current density of 1A/g, the specific capacitance of the composite material has reached 1021.5F/g.
Embodiment 2:
A kind of preparation method of MnS@CoMn-LDH composite material, comprising the following steps:
First step hydro-thermal, by 0.1g MnCl2·4H2O is dissolved in 25mL deionized water, is vigorously stirred lower addition 5mL
0.1mol/L Na2It after S, magnetic agitation 20min, is transferred in 50mL polytetrafluoroethyllining lining stainless steel autoclave, carries out first
Hydro-thermal reaction is walked, hydrothermal temperature is 150 DEG C, the hydro-thermal reaction time 8h；By after hydro-thermal sample take out cooling, then from
The heart, washing, 60 DEG C of vacuum drying 12h, obtain MnS powder.Second step hydro-thermal, by 1mmolMnCl2·4H2O、2mmol Co
(NO3)2·6H2O、5mmolNH4F, 5mmol urea is dissolved in deionized water, and after magnetic agitation 30min, first step water is added
MnS sample made from heat is transferred in polytetrafluoroethyllining lining stainless steel autoclave after mixing to it, carries out second step water
Thermal response, hydrothermal temperature are 120 DEG C, the hydro-thermal reaction time 6h；Sample after hydro-thermal is taken out into cooling, be then centrifuged for,
Washing, 60 DEG C of vacuum drying 12h, obtain MnS@CoMn-LDH powder.After the active material is ground, with carbon black, polytetrafluoro
Ethylene 8:1:1 in mass ratio is uniformly mixed, and is pressed together on foam nickel sheet (1cm × 1cm), and dry 12h, obtains in 60 DEG C of baking oven
MnS@CoMn-LDH working electrode (note MSCM-2).
The method for using cyclic voltammetry and constant current charge-discharge through occasion China CHI760e electrochemical workstation, using three electrodes
System: using the foam nickel sheet of MSCM-2 as working electrode, using Ag/AgCl electrode as reference electrode, with Pt electrode be to electrode, with
2mol/L KOH is electrolyte solution.The specific capacitance of the composite material and the performance of cyclical stability are detected, cyclic voltammetry is surveyed
Examination, it is shown that material has excellent redox ability.Fig. 4 is that the GCD of composite material schemes, it can be seen that in 2mol/L
In KOH solution and under the current density of 1A/g, the specific capacitance of the composite material has reached 968.25F/g.
Embodiment 3:
A kind of preparation method of MnS@CoMn-LDH composite material, comprising the following steps:
First step hydro-thermal, by 0.1g MnCl2·4H2O is dissolved in 25mL deionized water, is vigorously stirred lower addition 5mL
0.1mol/L Na2It after S, magnetic agitation 20min, is transferred in 50mL polytetrafluoroethyllining lining stainless steel autoclave, carries out first
Hydro-thermal reaction is walked, hydrothermal temperature is 120 DEG C, the hydro-thermal reaction time 12h；Sample after hydro-thermal is taken out into cooling, then
Centrifugation, washing, 60 DEG C of vacuum drying 12h, obtain MnS powder.Second step hydro-thermal, by 1mmolMnCl2·4H2O、2mmol Co
(NO3)2·6H2O、5mmolNH4F, 5mmol urea is dissolved in deionized water, and after magnetic agitation 30min, first step water is added
MnS sample made from heat is transferred in polytetrafluoroethyllining lining stainless steel autoclave after mixing to it, carries out second step water
Thermal response, hydrothermal temperature are 120 DEG C, the hydro-thermal reaction time 6h；Sample after hydro-thermal is taken out into cooling, be then centrifuged for,
Washing, 60 DEG C of vacuum drying 12h, obtain MnS@CoMn-LDH powder.After the active material is ground, with carbon black, polytetrafluoro
Ethylene 8:1:1 in mass ratio is uniformly mixed, and is pressed together on foam nickel sheet (1cm × 1cm), and dry 12h, obtains in 60 DEG C of baking oven
MnS@CoMn-LDH working electrode (note MSCM-3).
The method for using cyclic voltammetry and constant current charge-discharge through occasion China CHI760e electrochemical workstation, using three electrodes
System: using the foam nickel sheet of MSCM-3 as working electrode, using Ag/AgCl electrode as reference electrode, with Pt electrode be to electrode, with
2mol/L KOH is electrolyte solution.The specific capacitance of the composite material and the performance of cyclical stability are detected, cyclic voltammetry is surveyed
Examination, it is shown that material has excellent redox ability.In 2mol/L KOH solution and under the current density of 1A/g, this is multiple
The specific capacitance of condensation material has reached 921.25F/g.
Embodiment 4:
A kind of preparation method of MnS@CoMn-LDH composite material, comprising the following steps:
First step hydro-thermal, by 0.1g MnCl2·4H2O is dissolved in 25mL deionized water, is vigorously stirred lower addition 5mL
0.1mol/L Na2It after S, magnetic agitation 20min, is transferred in 50mL polytetrafluoroethyllining lining stainless steel autoclave, carries out first
Hydro-thermal reaction is walked, hydrothermal temperature is 120 DEG C, the hydro-thermal reaction time 8h；By after hydro-thermal sample take out cooling, then from
The heart, washing, 60 DEG C of vacuum drying 12h, obtain MnS powder.Second step hydro-thermal, by 1mmolMnCl2·4H2O、2mmol Co
(NO3)2·6H2O、5mmolNH4F, 5mmol urea is dissolved in deionized water, and after magnetic agitation 30min, first step water is added
MnS sample made from heat is transferred in polytetrafluoroethyllining lining stainless steel autoclave after mixing to it, carries out second step water
Thermal response, hydrothermal temperature are 120 DEG C, the hydro-thermal reaction time 6h；Sample after hydro-thermal is taken out into cooling, be then centrifuged for,
Washing, 60 DEG C of vacuum drying 12h, obtain MnS@CoMn-LDH powder.After the active material is ground, with carbon black, polytetrafluoro
Ethylene 8:1:1 in mass ratio is uniformly mixed, and is pressed together on foam nickel sheet (1cm × 1cm), and dry 12h, obtains in 60 DEG C of baking oven
MnS@CoMn-LDH working electrode (note MSCM-4).
The method for using cyclic voltammetry and constant current charge-discharge through occasion China CHI760e electrochemical workstation, using three electrodes
System: using the foam nickel sheet of MSCM-4 as working electrode, using Ag/AgCl electrode as reference electrode, with Pt electrode be to electrode, with
2mol/L KOH is electrolyte solution.The specific capacitance of the composite material and the performance of cyclical stability are detected, cyclic voltammetry is surveyed
Examination, it is shown that material has excellent redox ability.In 2mol/L KOH solution and under the current density of 1A/g, this is multiple
The specific capacitance of condensation material has reached 1011.5F/g.
Embodiment 5:
A kind of preparation method of MnS@CoMn-LDH composite material, comprising the following steps:
First step hydro-thermal, by 0.1g MnCl2·4H2O is dissolved in 25mL deionized water, is vigorously stirred lower addition 5mL
0.1mol/L Na2It after S, magnetic agitation 20min, is transferred in 50mL polytetrafluoroethyllining lining stainless steel autoclave, carries out first
Hydro-thermal reaction is walked, hydrothermal temperature is 120 DEG C, the hydro-thermal reaction time 8h；By after hydro-thermal sample take out cooling, then from
The heart, washing, 60 DEG C of vacuum drying 12h, obtain MnS powder.Second step hydro-thermal, by 1mmolMnCl2·4H2O、2mmol Co
(NO3)2·6H2O、5mmolNH4F, 5mmol urea is dissolved in deionized water, and after magnetic agitation 30min, first step water is added
MnS sample made from heat is transferred in polytetrafluoroethyllining lining stainless steel autoclave after mixing to it, carries out second step water
Thermal response, hydrothermal temperature are 150 DEG C, the hydro-thermal reaction time 6h；Sample after hydro-thermal is taken out into cooling, be then centrifuged for,
Washing, 60 DEG C of vacuum drying 12h, obtain MnS@CoMn-LDH powder.After the active material is ground, with carbon black, polytetrafluoro
Ethylene 8:1:1 in mass ratio is uniformly mixed, and is pressed together on foam nickel sheet (1cm × 1cm), and dry 12h, obtains in 60 DEG C of baking oven
MnS@CoMn-LDH working electrode (note MSCM-5).
The method for using cyclic voltammetry and constant current charge-discharge through occasion China CHI760e electrochemical workstation, using three electrodes
System: using the foam nickel sheet of MSCM-5 as working electrode, using Ag/AgCl electrode as reference electrode, with Pt electrode be to electrode, with
2mol/L KOH is electrolyte solution.The specific capacitance of the composite material and the performance of cyclical stability are detected, cyclic voltammetry is surveyed
Examination, it is shown that material has excellent redox ability.In 2mol/L KOH solution and under the current density of 1A/g, this is multiple
The specific capacitance of condensation material has reached 960.5F/g.
Embodiment 6:
A kind of preparation method of MnS@CoMn-LDH composite material, comprising the following steps:
First step hydro-thermal, by 0.1g MnCl2·4H2O is dissolved in 25mL deionized water, is vigorously stirred lower addition 5mL
0.1mol/L Na2It after S, magnetic agitation 20min, is transferred in 50mL polytetrafluoroethyllining lining stainless steel autoclave, carries out first
Hydro-thermal reaction is walked, hydrothermal temperature is 120 DEG C, the hydro-thermal reaction time 8h；By after hydro-thermal sample take out cooling, then from
The heart, washing, 60 DEG C of vacuum drying 12h, obtain MnS powder.Second step hydro-thermal, by 1mmolMnCl2·4H2O、2mmol Co
(NO3)2·6H2O、5mmolNH4F, 5mmol urea is dissolved in deionized water, and after magnetic agitation 30min, first step water is added
MnS sample made from heat is transferred in polytetrafluoroethyllining lining stainless steel autoclave after mixing to it, carries out second step water
Thermal response, hydrothermal temperature are 120 DEG C, the hydro-thermal reaction time 10h；Sample after hydro-thermal is taken out into cooling, be then centrifuged for,
Washing, 60 DEG C of vacuum drying 12h, obtain MnS@CoMn-LDH powder.After the active material is ground, with carbon black, polytetrafluoro
Ethylene 8:1:1 in mass ratio is uniformly mixed, and is pressed together on foam nickel sheet (1cm × 1cm), and dry 12h, obtains in 60 DEG C of baking oven
MnS@CoMn-LDH working electrode (note MSCM-6).
The method for using cyclic voltammetry and constant current charge-discharge through occasion China CHI760e electrochemical workstation, using three electrodes
System: using the foam nickel sheet of MSCM-6 as working electrode, using Ag/AgCl electrode as reference electrode, with Pt electrode be to electrode, with
2mol/L KOH is electrolyte solution.The specific capacitance of the composite material and the performance of cyclical stability are detected, cyclic voltammetry is surveyed
Examination, it is shown that material has excellent redox ability.In 2mol/L KOH solution and under the current density of 1A/g, this is multiple
The specific capacitance of condensation material has reached 981.75F/g.
Embodiment 7:
A kind of MnS@CoMn-LDH composite material, preparation method includes the following steps:
1) manganous chloride is soluble in water, vulcanized sodium is added later, and a hydro-thermal reaction 16h is carried out at 120 DEG C, after
Through centrifugation, washing, drying, MnS is obtained；
2) by manganous chloride, cobalt nitrate, ammonium fluoride and urea (manganous chloride, cobalt nitrate, ammonium fluoride and urea soluble in water
Molar ratio be 1:1.8:6:4), MnS is added later, and secondary hydro-thermal reaction 6h is carried out at 180 DEG C, by cooling, centrifugation,
Washing, and 10h is dried in vacuo at 65 DEG C to get MnS@CoMn-LDH composite material is arrived.
Composite material is prepared into working electrode, in supercapacitor.The preparation process of working electrode are as follows: will be compound
It after material grinding, is uniformly mixed with carbon black and polytetrafluoroethylene (PTFE), is pressed together on nickel foam on piece later, at 70 DEG C after dry 10h
Obtain working electrode.Wherein, the mass ratio of composite material, carbon black and polytetrafluoroethylene (PTFE) is 8:1.2:0.8.
Embodiment 8:
A kind of MnS@CoMn-LDH composite material, preparation method includes the following steps:
1) manganous chloride is soluble in water, vulcanized sodium is added later, and a hydro-thermal reaction 8h is carried out at 180 DEG C, after
Through centrifugation, washing, drying, MnS is obtained；
2) by manganous chloride, cobalt nitrate, ammonium fluoride and urea (manganous chloride, cobalt nitrate, ammonium fluoride and urea soluble in water
Molar ratio be 1:2.2:4:6), MnS is added later, and secondary hydro-thermal reaction 12h is carried out at 120 DEG C, by cooling, from
The heart, washing, and 14h is dried in vacuo at 55 DEG C to get MnS@CoMn-LDH composite material is arrived.
Composite material is prepared into working electrode, in supercapacitor.The preparation process of working electrode are as follows: will be compound
It after material grinding, is uniformly mixed with carbon black and polytetrafluoroethylene (PTFE), is pressed together on nickel foam on piece later, at 50 DEG C after dry 15h
Obtain working electrode.Wherein, the mass ratio of composite material, carbon black and polytetrafluoroethylene (PTFE) is 8:0.8:1.2.
Embodiment 9:
A kind of MnS@CoMn-LDH composite material, preparation method includes the following steps:
1) manganous chloride is soluble in water, vulcanized sodium is added later, and a hydro-thermal reaction 12h is carried out at 150 DEG C, after
Through centrifugation, washing, drying, MnS is obtained；
2) by manganous chloride, cobalt nitrate, ammonium fluoride and urea (manganous chloride, cobalt nitrate, ammonium fluoride and urea soluble in water
Molar ratio be 1:1:5:5), MnS is added later, and carry out secondary hydro-thermal reaction 9h at 150 DEG C, by cooling, is centrifuged, washes
It washs, and is dried in vacuo 12h at 60 DEG C to get MnS@CoMn-LDH composite material is arrived.
Composite material is prepared into working electrode, in supercapacitor.The preparation process of working electrode are as follows: will be compound
It after material grinding, is uniformly mixed with carbon black and polytetrafluoroethylene (PTFE), is pressed together on nickel foam on piece later, at 60 DEG C after dry 12h
Obtain working electrode.Wherein, the mass ratio of composite 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 MnS@CoMn-LDH composite material, which is characterized in that method includes the following steps:
1) soluble manganese salt is soluble in water, sulfide is added later, and carry out a hydro-thermal reaction, by centrifugation, washing, does
It is dry, obtain MnS；
2) soluble manganese salt, soluble cobalt, ammonium fluoride and urea is soluble in water, MnS is added later, and carry out secondary water heat
Reaction arrives the MnS@CoMn-LDH composite material by cooling, centrifugation, washing, drying.
2. a kind of preparation method of MnS@CoMn-LDH composite material according to claim 1, which is characterized in that described
Soluble manganese salt is manganous chloride, and the sulfide is vulcanized sodium, and the soluble cobalt is cobalt nitrate.
3. a kind of preparation method of MnS@CoMn-LDH composite material according to claim 1, which is characterized in that step 1)
In, in a hydrothermal reaction process, temperature is 120-180 DEG C, time 8-16h；In step 2), the secondary water
In thermal process reactor, temperature is 120-180 DEG C, time 6-12h.
4. a kind of preparation method of MnS@CoMn-LDH composite material according to claim 1, which is characterized in that described
Dry is vacuum drying, and in the drying process, and temperature is 55-65 DEG C, time 10-14h.
5. a kind of preparation method of MnS@CoMn-LDH composite material according to claim 1, which is characterized in that step 2)
In, the soluble manganese salt, soluble cobalt, the molar ratio of ammonium fluoride and urea are 1:(1.8-2.2): (4-6): (4-6).
6. a kind of MnS@CoMn-LDH composite material, which is characterized in that the composite material is used such as any one of claim 1 to 5
The method is prepared.
7. a kind of application of MnS@CoMn-LDH composite material as claimed in claim 6, which is characterized in that will be described compound
Material is prepared into working electrode, in supercapacitor.
8. a kind of application of MnS@CoMn-LDH composite material according to claim 7, which is characterized in that the work
The preparation process of electrode are as follows: after grinding composite material, be uniformly mixed with carbon black and polytetrafluoroethylene (PTFE), be pressed together on nickel foam later
On piece obtains the working electrode after drying.
9. a kind of application of MnS@CoMn-LDH composite material according to claim 8, which is characterized in that described is compound
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 MnS@CoMn-LDH composite material according to claim 8, which is characterized in that described is dry
During dry, temperature is 50-70 DEG C, time 10-15h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110813321A (en) * | 2019-11-05 | 2020-02-21 | 沈阳工业大学 | Preparation method and application of Ag-supported MnS embedded flexible electrode material |
| CN111276340A (en) * | 2020-01-23 | 2020-06-12 | 上海应用技术大学 | Ce-Co-S composite material and preparation method and application thereof |
| CN111333129A (en) * | 2020-02-28 | 2020-06-26 | 上海应用技术大学 | Preparation method of nano nickel sulfide/nitrogen-doped porous carbon composite material for super capacitor |
| CN111840548A (en) * | 2020-07-17 | 2020-10-30 | 华侨大学 | Preparation method of layered double hydroxide nanosheet-copper sulfide quantum dot heterogeneous nano complex |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107731566A (en) * | 2017-10-21 | 2018-02-23 | 福州大学 | A kind of preparation method and application of three-dimensional petal-shaped nickel cobalt sulfide electrode material |
| CN108538622A (en) * | 2018-06-14 | 2018-09-14 | 长沙理工大学 | The preparation method of nickel foam self-supporting MnS nanometer sheet super capacitor materials |
| CN109225270A (en) * | 2018-09-30 | 2019-01-18 | 陕西科技大学 | A kind of Ni3S2@NiV-LDH heterojunction structure bifunctional electrocatalyst, Preparation method and use |
| WO2019106466A1 (en) * | 2017-11-30 | 2019-06-06 | Sabic Global Technologies B.V. | Two-dimensional transition metal oxide and semiconducting polymer hybrids with electro-activity and photosensitivity |
-
2019
- 2019-06-14 CN CN201910517909.7A patent/CN110211812B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107731566A (en) * | 2017-10-21 | 2018-02-23 | 福州大学 | A kind of preparation method and application of three-dimensional petal-shaped nickel cobalt sulfide electrode material |
| WO2019106466A1 (en) * | 2017-11-30 | 2019-06-06 | Sabic Global Technologies B.V. | Two-dimensional transition metal oxide and semiconducting polymer hybrids with electro-activity and photosensitivity |
| CN108538622A (en) * | 2018-06-14 | 2018-09-14 | 长沙理工大学 | The preparation method of nickel foam self-supporting MnS nanometer sheet super capacitor materials |
| CN109225270A (en) * | 2018-09-30 | 2019-01-18 | 陕西科技大学 | A kind of Ni3S2@NiV-LDH heterojunction structure bifunctional electrocatalyst, Preparation method and use |
Non-Patent Citations (1)
| Title |
|---|
| JIAN WANG: "Preparation of Molybdenum Disulfide Coated Mg/Al Layered Double", 《ACS SUSTAINABLE CHEM. ENG.》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110813321A (en) * | 2019-11-05 | 2020-02-21 | 沈阳工业大学 | Preparation method and application of Ag-supported MnS embedded flexible electrode material |
| CN110813321B (en) * | 2019-11-05 | 2022-05-13 | 沈阳工业大学 | Preparation method and application of Ag-supported MnS embedded flexible electrode material |
| CN111276340A (en) * | 2020-01-23 | 2020-06-12 | 上海应用技术大学 | Ce-Co-S composite material and preparation method and application thereof |
| CN111276340B (en) * | 2020-01-23 | 2022-05-17 | 上海应用技术大学 | Ce-Co-S composite material and preparation method and application thereof |
| CN111333129A (en) * | 2020-02-28 | 2020-06-26 | 上海应用技术大学 | Preparation method of nano nickel sulfide/nitrogen-doped porous carbon composite material for super capacitor |
| CN111333129B (en) * | 2020-02-28 | 2022-08-23 | 上海应用技术大学 | Preparation method of nano nickel sulfide/nitrogen-doped porous carbon composite material for super capacitor |
| CN111840548A (en) * | 2020-07-17 | 2020-10-30 | 华侨大学 | Preparation method of layered double hydroxide nanosheet-copper sulfide quantum dot heterogeneous nano complex |
| CN111840548B (en) * | 2020-07-17 | 2022-06-07 | 华侨大学 | Preparation method of layered double hydroxide nanosheet-copper sulfide quantum dot heterogeneous nano complex |
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