CN110211812B - MnS @ CoMn-LDH composite material and preparation method and application thereof - Google Patents
MnS @ CoMn-LDH composite material and preparation method and application thereof Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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Abstract
The invention relates to a MnS @ CoMn-LDH composite material and a preparation method and application thereof, wherein the preparation method of the composite material comprises the following steps: 1) dissolving soluble manganese salt in water, adding sulfide, carrying out a hydrothermal reaction, centrifuging, washing and drying to obtain MnS; 2) dissolving soluble manganese salt, soluble cobalt salt, ammonium fluoride and urea in water, adding MnS, performing secondary hydrothermal reaction, cooling, centrifuging, washing and drying to obtain the MnS @ CoMn-LDH composite material; the composite material is prepared into a working electrode for being used in a super capacitor. Compared with the prior art, the MnS @ CoMn-LDH composite material is synthesized by two hydrothermal steps, the composite material contains abundant mesopores and micropores so as to achieve good electrochemical performance, the preparation method of the composite material is simple and environment-friendly, the synthesis time is greatly shortened, and the high-purity MnS @ CoMn-LDH composite material is convenient to produce on a large scale.
Description
Technical Field
The invention belongs to the technical field of electrochemistry and nano materials, and relates to a MnS @ CoMn-LDH composite material, a preparation method thereof and application thereof in a super capacitor.
Background
With the increasing environmental pollution and fossil fuel consumption, the development of renewable energy storage devices is becoming more and more important. Super capacitors, also called electrochemical capacitors, have drawn attention from the industry and academia due to their advantages of high power density, high rate capability, fast charge and discharge process, long cycle life (>10 ten thousand times). The performance of supercapacitors depends essentially on the performance of the electrode material. In recent years, transition metal oxides, sulfides and hydroxides have been widely studied as electrode materials for battery-type supercapacitors because of their high theoretical specific capacitance. Among the numerous battery-like materials, transition metal sulfides have received much attention as highly efficient HSC electrode materials, mainly because of their smaller band gap, superior electrochemical performance, and higher electrical conductivity compared to the corresponding metal oxides.
In recent years, CoS2、CuS、Ni3S2、CoNi2S4、MoS2、FeS2And the like, have been widely studied and can serve as reliable electrode materials for supercapacitor applications. It has higher conductivity and better cycle performance than metal oxides. Of the various metal sulfides, MnS is a p-type semiconductor with a band gap of 3.1-3.7eV, which has higher conductivity than the corresponding metal oxide or metal hydroxide. MnS may exhibit three polymorphs: α, β, γ -MnS. Among the three polymorphs, green α -MnS is in the rock salt structure with better stability than the other two polymorphs; pink beta-MnS and gamma-MnS are in sphalerite and wurtzite structures respectively and are metastable.
Transition metal Layered Double Hydroxide (LDH) as a two-dimensional (2D) material has a special layered structure. Their high surface area and fast ion transfer rates facilitate their use in energy conversion and storage. However, the aggregation and low conductivity of LDHs limit the transport of ions/electrons, leading to non-ideal electrochemical performance, limiting its further applications.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a MnS @ CoMn-LDH composite material and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a MnS @ CoMn-LDH composite material comprises the following steps:
1) dissolving soluble manganese salt in water, adding sulfide, carrying out a hydrothermal reaction, centrifuging, washing and drying to obtain MnS;
2) dissolving soluble manganese salt, soluble cobalt salt, ammonium fluoride and urea in water, adding MnS, carrying out secondary hydrothermal reaction, cooling, centrifuging, washing and drying to obtain the MnS @ CoMn-LDH composite material.
Further, the soluble manganese salt is manganese dichloride, the sulfide is sodium sulfide, and the soluble cobalt salt is cobalt nitrate.
Further, in the step 1), the temperature is 120-180 ℃ and the time is 8-16h in the primary hydrothermal reaction process; in the step 2), the temperature is 120-180 ℃ and the time is 6-12h in the secondary hydrothermal reaction process.
Further, the drying is vacuum drying, and in the drying process, the temperature is 55-65 ℃ and the time is 10-14 h.
Further, in the step 2), the mol ratio of the soluble manganese salt, the soluble cobalt salt, the ammonium fluoride and the urea is 1 (1.8-2.2) to (4-6).
The MnS @ CoMn-LDH composite material is prepared by adopting the method.
The application of the MnS @ CoMn-LDH composite material is to prepare the composite material into a working electrode for a super capacitor.
Further, the preparation process of the working electrode comprises the following steps: grinding the composite material, uniformly mixing the ground composite material with carbon black and polytetrafluoroethylene, then pressing the mixture on a foam nickel sheet, and drying to obtain the working electrode.
Furthermore, the mass ratio of the composite material, the carbon black and the polytetrafluoroethylene is 8 (0.8-1.2) to (0.8-1.2).
Furthermore, in the drying process, the temperature is 50-70 ℃ and the time is 10-15 h.
In the preparation process of the MnS @ CoMn-LDH composite material, the hydrolysis reaction of urea in the hydrothermal process enables Mn to be obtained2+And Co2+With OH-Reacting to generate a CoMn-LDH nano structure; fluorine ions in the ammonium fluoride can be selectively adsorbed on crystal faces, so that the crystallization dynamics behavior of each crystal face is changed, finally, the crystals have the difference in appearance, and low-concentration NH is generated4 +Will inhibit OH-The growth rate of the CoMn-LDH is reduced, and crystals grow along a specific lattice orientation to form CoMn-LDH nano-needles.
Compared with the prior art, the invention has the following characteristics:
1) the MnS @ CoMn-LDH composite material is hydrothermally synthesized by two steps, contains rich mesopores and micropores so as to achieve good electrochemical performance, is simple in preparation method and environment-friendly, greatly shortens the synthesis time, and facilitates large-scale production of the high-purity MnS @ CoMn-LDH composite material;
2) the composite material prepared by the hydrothermal reaction has a unique core-shell structure, and the thin LDH nano sheet is used as a shell material of a one-dimensional core-shell structure, has a larger surface area, and can provide rich electrolyte diffusion channels, so that sufficient electroactive sites and rich electrolyte diffusion channels can be provided by utilizing the synergistic effect of the two components;
3) the working electrode prepared from the MnS @ CoMn-LDH composite material has high current density, is used in a super capacitor, and is beneficial to rapid transmission of electrons.
Drawings
FIG. 1 is a preparation scheme of MnS @ CoMn-LDH composite material;
FIG. 2 is a cyclic voltammogram of the MnS @ CoMn-LDH composite material prepared in example 1 at different sweep rates;
FIG. 3 is a GCD plot of the MnS @ CoMn-LDH composite material prepared in example 1 at a current density of 1A/g;
FIG. 4 is a GCD plot of the MnS @ CoMn-LDH composite material prepared in example 2 at a current density of 1A/g.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The raw materials used in the examples are commercially available unless otherwise specified.
Example 1:
a preparation method of the MnS @ CoMn-LDH composite material is shown in figure 1 and comprises the following steps:
in the first hydrothermal step, 0.1g of MnCl is added2·4H2O was dissolved in 25mL of deionized water, and 5mL of 0.1mol/L Na was added with vigorous stirring2S, magnetically stirring for 20min, transferring to a 50mL stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out a first-step hydrothermal reaction at 120 ℃ for 8 h; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain MnS powder. The second step is hydrothermal, 1mmol of MnCl is added2·4H2O、2mmol Co(NO3)2·6H2O、5mmolNH4F. Dissolving 5mmol of urea in deionized water, magnetically stirring for 30min, adding the MnS sample prepared in the first hydrothermal step, uniformly mixing, transferring to a polytetrafluoroethylene-lined stainless steel autoclave, and carrying out a second hydrothermal reaction at 120 ℃ for 6 h; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain MnS @ CoMn-LDH powder. Grinding the active material, mixing with carbon black and polytetrafluoroethyleneThe alkene is uniformly mixed according to the mass ratio of 8:1:1, pressed on a foam nickel sheet (1cm multiplied by 1cm), and dried for 12h in a drying oven at the temperature of 60 ℃ to obtain the MnS @ CoMn-LDH working electrode (recorded as MSCM-1).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: the method comprises the following steps of taking a foam nickel sheet of MSCM-1 as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a Pt electrode as a counter electrode and taking 2mol/L KOH as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and the cyclic voltammetry test result is shown in figure 2, which shows that the composite material has excellent oxidation-reduction capability. FIG. 3 is a GCD graph of the composite material, and it can be seen that the specific capacitance of the composite material reached 1021.5F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 2:
a preparation method of a MnS @ CoMn-LDH composite material comprises the following steps:
in the first hydrothermal step, 0.1g of MnCl is added2·4H2O was dissolved in 25mL of deionized water, and 5mL of 0.1mol/L Na was added with vigorous stirring2S, magnetically stirring for 20min, transferring to a 50mL stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out a first-step hydrothermal reaction at 150 ℃ for 8 h; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain MnS powder. The second step is hydrothermal, 1mmol of MnCl is added2·4H2O、2mmol Co(NO3)2·6H2O、5mmolNH4F. Dissolving 5mmol of urea in deionized water, magnetically stirring for 30min, adding the MnS sample prepared in the first hydrothermal step, uniformly mixing, transferring to a polytetrafluoroethylene-lined stainless steel autoclave, and carrying out a second hydrothermal reaction at 120 ℃ for 6 h; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain MnS @ CoMn-LDH powder. Grinding the active material, uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1, pressing the mixture on a foam nickel sheet (1cm multiplied by 1cm), and drying the foam nickel sheet in a drying oven at the temperature of 60 ℃ for 12 hours to obtain a MnS @ CoMn-LDH working electrode (MSCM-2).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: the method comprises the following steps of taking a foam nickel sheet of MSCM-2 as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a Pt electrode as a counter electrode and taking 2mol/L KOH as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. FIG. 4 is a GCD plot of the composite material, and it can be seen that the specific capacitance of the composite material reached 968.25F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 3:
a preparation method of a MnS @ CoMn-LDH composite material comprises the following steps:
in the first hydrothermal step, 0.1g of MnCl is added2·4H2O was dissolved in 25mL of deionized water, and 5mL of 0.1mol/L Na was added with vigorous stirring2S, magnetically stirring for 20min, transferring to a 50mL stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out a first-step hydrothermal reaction at 120 ℃ for 12 h; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain MnS powder. The second step is hydrothermal, 1mmol of MnCl is added2·4H2O、2mmol Co(NO3)2·6H2O、5mmolNH4F. Dissolving 5mmol of urea in deionized water, magnetically stirring for 30min, adding the MnS sample prepared in the first hydrothermal step, uniformly mixing, transferring to a polytetrafluoroethylene-lined stainless steel autoclave, and carrying out a second hydrothermal reaction at 120 ℃ for 6 h; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain MnS @ CoMn-LDH powder. Grinding the active material, uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1, pressing the mixture on a foam nickel sheet (1cm multiplied by 1cm), and drying the foam nickel sheet in a drying oven at the temperature of 60 ℃ for 12 hours to obtain a MnS @ CoMn-LDH working electrode (recorded as MSCM-3).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: the method comprises the following steps of taking a foam nickel sheet of MSCM-3 as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a Pt electrode as a counter electrode and taking 2mol/L KOH as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the composite material reaches 921.25F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 4:
a preparation method of a MnS @ CoMn-LDH composite material comprises the following steps:
in the first hydrothermal step, 0.1g of MnCl is added2·4H2O was dissolved in 25mL of deionized water, and 5mL of 0.1mol/L Na was added with vigorous stirring2S, magnetically stirring for 20min, transferring to a 50mL stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out a first-step hydrothermal reaction at 120 ℃ for 8 h; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain MnS powder. The second step is hydrothermal, 1mmol of MnCl is added2·4H2O、2mmol Co(NO3)2·6H2O、5mmolNH4F. Dissolving 5mmol of urea in deionized water, magnetically stirring for 30min, adding the MnS sample prepared in the first hydrothermal step, uniformly mixing, transferring to a polytetrafluoroethylene-lined stainless steel autoclave, and carrying out a second hydrothermal reaction at 120 ℃ for 6 h; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain MnS @ CoMn-LDH powder. Grinding the active material, uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1, pressing the mixture on a foam nickel sheet (1cm multiplied by 1cm), and drying the foam nickel sheet in a drying oven at the temperature of 60 ℃ for 12 hours to obtain a MnS @ CoMn-LDH working electrode (recorded as MSCM-4).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: the method comprises the following steps of taking a foam nickel sheet of MSCM-4 as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a Pt electrode as a counter electrode and taking 2mol/L KOH as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the composite material reaches 1011.5F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 5:
a preparation method of a MnS @ CoMn-LDH composite material comprises the following steps:
in the first hydrothermal step, 0.1g of MnCl is added2·4H2O was dissolved in 25mL of deionized water, and 5mL of 0.1mol/L Na was added with vigorous stirring2S, magnetically stirring for 20min, transferring to a 50mL stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out a first-step hydrothermal reaction at 120 ℃ for 8 h; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain MnS powder. The second step is hydrothermal, 1mmol of MnCl is added2·4H2O、2mmol Co(NO3)2·6H2O、5mmolNH4F. Dissolving 5mmol of urea in deionized water, magnetically stirring for 30min, adding the MnS sample prepared in the first hydrothermal step, uniformly mixing, transferring to a polytetrafluoroethylene-lined stainless steel autoclave, and carrying out a second hydrothermal reaction at 150 ℃ for 6 h; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain MnS @ CoMn-LDH powder. Grinding the active material, uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1, pressing the mixture on a foam nickel sheet (1cm multiplied by 1cm), and drying the foam nickel sheet in a drying oven at the temperature of 60 ℃ for 12 hours to obtain a MnS @ CoMn-LDH working electrode (MSCM-5).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: the method comprises the following steps of taking a foam nickel sheet of MSCM-5 as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a Pt electrode as a counter electrode and taking 2mol/L KOH as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the composite material reaches 960.5F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 6:
a preparation method of a MnS @ CoMn-LDH composite material comprises the following steps:
in the first hydrothermal step, 0.1g of MnCl is added2·4H2O was dissolved in 25mL of deionized water, and 5mL of 0.1mol/L Na was added with vigorous stirring2S, magnetically stirring for 20min, transferring to a 50mL stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out a first-step hydrothermal reaction at 120 ℃ for 8 h; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain MnS powder. The second step is hydrothermal, 1mmol of MnCl is added2·4H2O、2mmol Co(NO3)2·6H2O、5mmolNH4F. Dissolving 5mmol of urea in deionized water, magnetically stirring for 30min, adding the MnS sample prepared in the first hydrothermal step, uniformly mixing, transferring to a polytetrafluoroethylene-lined stainless steel autoclave, and carrying out a second hydrothermal reaction at 120 ℃ for 10 h; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain MnS @ CoMn-LDH powder. Grinding the active material, uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1, pressing the mixture on a foam nickel sheet (1cm multiplied by 1cm), and drying the foam nickel sheet in a drying oven at the temperature of 60 ℃ for 12 hours to obtain a MnS @ CoMn-LDH working electrode (MSCM-6).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: the method comprises the following steps of taking a foam nickel sheet of MSCM-6 as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a Pt electrode as a counter electrode and taking 2mol/L KOH as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the composite material reaches 981.75F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 7:
the preparation method of the MnS @ CoMn-LDH composite material comprises the following steps:
1) dissolving manganese dichloride in water, adding sodium sulfide, carrying out a hydrothermal reaction for 16 hours at 120 ℃, and then centrifuging, washing and drying to obtain MnS;
2) dissolving manganese dichloride, cobalt nitrate, ammonium fluoride and urea in water (the molar ratio of the manganese dichloride, the cobalt nitrate, the ammonium fluoride and the urea is 1:1.8:6:4), then adding MnS, carrying out secondary hydrothermal reaction at 180 ℃ for 6h, cooling, centrifuging, washing, and drying in vacuum at 65 ℃ for 10h to obtain the MnS @ CoMn-LDH composite material.
The composite material is prepared into a working electrode for being used in a super capacitor. The preparation process of the working electrode comprises the following steps: grinding the composite material, uniformly mixing the ground composite material with carbon black and polytetrafluoroethylene, then pressing the mixture on a foam nickel sheet, and drying the foam nickel sheet at 70 ℃ for 10 hours to obtain the working electrode. Wherein the mass ratio of the composite material, the carbon black and the polytetrafluoroethylene is 8:1.2: 0.8.
Example 8:
the preparation method of the MnS @ CoMn-LDH composite material comprises the following steps:
1) dissolving manganese dichloride in water, adding sodium sulfide, carrying out a hydrothermal reaction for 8 hours at 180 ℃, and then centrifuging, washing and drying to obtain MnS;
2) dissolving manganese dichloride, cobalt nitrate, ammonium fluoride and urea in water (the molar ratio of the manganese dichloride, the cobalt nitrate, the ammonium fluoride and the urea is 1:2.2:4:6), adding MnS, carrying out secondary hydrothermal reaction at 120 ℃ for 12h, cooling, centrifuging, washing, and carrying out vacuum drying at 55 ℃ for 14h to obtain the MnS @ CoMn-LDH composite material.
The composite material is prepared into a working electrode for being used in a super capacitor. The preparation process of the working electrode comprises the following steps: grinding the composite material, uniformly mixing the ground composite material with carbon black and polytetrafluoroethylene, then pressing the mixture on a foam nickel sheet, and drying the foam nickel sheet at 50 ℃ for 15 hours to obtain the working electrode. Wherein the mass ratio of the composite material, the carbon black and the polytetrafluoroethylene is 8:0.8: 1.2.
Example 9:
the preparation method of the MnS @ CoMn-LDH composite material comprises the following steps:
1) dissolving manganese dichloride in water, adding sodium sulfide, carrying out a hydrothermal reaction for 12 hours at 150 ℃, and then centrifuging, washing and drying to obtain MnS;
2) dissolving manganese dichloride, cobalt nitrate, ammonium fluoride and urea in water (the molar ratio of the manganese dichloride, the cobalt nitrate, the ammonium fluoride and the urea is 1:1:5:5), adding MnS, carrying out secondary hydrothermal reaction for 9h at 150 ℃, cooling, centrifuging, washing, and drying in vacuum for 12h at 60 ℃ to obtain the MnS @ CoMn-LDH composite material.
The composite material is prepared into a working electrode for being used in a super capacitor. The preparation process of the working electrode comprises the following steps: grinding the composite material, uniformly mixing the ground composite material with carbon black and polytetrafluoroethylene, then pressing the mixture on a foam nickel sheet, and drying the foam nickel sheet at 60 ℃ for 12 hours to obtain the working electrode. Wherein the mass ratio of the composite material, the carbon black and the polytetrafluoroethylene is 8:1: 1.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a MnS @ CoMn-LDH composite material is characterized by comprising the following steps:
1) dissolving soluble manganese salt in water, adding sulfide, carrying out a hydrothermal reaction, centrifuging, washing and drying to obtain MnS;
2) dissolving soluble manganese salt, soluble cobalt salt, ammonium fluoride and urea in water, adding MnS, performing secondary hydrothermal reaction, cooling, centrifuging, washing and drying to obtain the MnS @ CoMn-LDH composite material;
the LDH is a layered dihydroxy compound.
2. The method of claim 1, wherein said soluble manganese salt is manganese dichloride, said sulfide is sodium sulfide, and said soluble cobalt salt is cobalt nitrate.
3. The preparation method of the MnS @ CoMn-LDH composite material as claimed in claim 1, wherein in the step 1), the temperature is 120-180 ℃ and the time is 8-16h in the primary hydrothermal reaction process; in the step 2), the temperature is 120-180 ℃ and the time is 6-12h in the secondary hydrothermal reaction process.
4. The method for preparing a MnS @ CoMn-LDH composite material as claimed in claim 1, wherein said drying is vacuum drying, and the temperature during said drying is 55-65 ℃ for 10-14 h.
5. The method for preparing a MnS @ CoMn-LDH composite material as claimed in claim 1, wherein the molar ratio of the soluble manganese salt, the soluble cobalt salt, the ammonium fluoride and the urea in step 2) is 1 (1.8-2.2): (4-6): (4-6).
6. A MnS @ CoMn-LDH composite material prepared by the method as set forth in any one of claims 1 to 5.
7. Use of the MnS @ CoMn-LDH composite material of claim 6, in the preparation of a working electrode for use in a supercapacitor.
8. The use of a MnS @ CoMn-LDH composite material as claimed in claim 7, wherein said working electrode is prepared by: grinding the composite material, uniformly mixing the ground composite material with carbon black and polytetrafluoroethylene, then pressing the mixture on a foam nickel sheet, and drying to obtain the working electrode.
9. The use of a MnS @ CoMn-LDH composite material as claimed in claim 8, wherein the mass ratio of the composite material to the carbon black to the polytetrafluoroethylene is 8 (0.8-1.2) to (0.8-1.2).
10. The use of a MnS @ CoMn-LDH composite material as claimed in claim 8, wherein said drying is carried out at a temperature of 50-70 ℃ for a period of 10-15 hours.
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| 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 |
| 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 |
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