CN110808172A - Fe-Co-S nanosheet material and preparation method and application thereof - Google Patents
Fe-Co-S nanosheet material and preparation method and application thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 44
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 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 8
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 44
- 239000002131 composite material Substances 0.000 claims description 31
- -1 polytetrafluoroethylene Polymers 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 239000006260 foam Substances 0.000 claims description 20
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 239000006229 carbon black Substances 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 150000002505 iron Chemical class 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 15
- 239000011149 active material Substances 0.000 description 13
- 229910021607 Silver chloride Inorganic materials 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 7
- 238000010277 constant-current charging Methods 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 6
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 229910002546 FeCo Inorganic materials 0.000 description 2
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002057 nanoflower Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- 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
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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
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- B82Y40/00—Manufacture or treatment of nanostructures
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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- 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 Fe-Co-S nanosheet material as well as a preparation method and application thereof, wherein the preparation method comprises the following steps: s1: dissolving soluble cobalt salt, soluble ferric salt, urea and ammonium fluoride in water, stirring uniformly, adding thiourea, and carrying out hydrothermal reaction; s2: and after the hydrothermal reaction is finished, cooling, centrifuging, washing and drying to obtain the Fe-Co-S nanosheet material. Compared with the prior art, the Fe-Co-S nanosheet material is synthesized through one-step hydrothermal synthesis, has a porous nanostructure with a high effective specific surface area, can provide more electrochemical active sites and a rapid ion transportation way, is simple in preparation method and environment-friendly, greatly shortens the synthesis time, and is convenient for large-scale production of the Fe-Co-S nanosheet material.
Description
Technical Field
The invention relates to the technical field of electrochemistry and nano materials, in particular to a Fe-Co-S nano sheet material and a preparation method and application thereof.
Background
Increasing concern over global environmental issues and depletion of fossil energy resources have prompted intensive research into renewable energy forms and energy storage devices. Super Capacitors (SCs) have the unique characteristics of fast charge and discharge, long cycle life, and high power density, and have received extensive research interest as ideal energy storage systems for electric vehicles and portable electronic devices. Among different super capacitors, the pseudo capacitor releases higher capacitance than electrochemical double-layer capacitors (EDLCs) through rapid reversible surface Faraday redox reactions on electrodes, and has great potential for developing high-energy storage super capacitors. Today, many capacitive materials, including conductive polymers (polyaniline (PANI), polypyrrole (PPy) and poly (3,4 ethylenedioxythiophene)), transition metal oxides (MnO), are available2、Co3O4、V2O5NiO, etc.) and transition metal hydroxides (Ni (OH)2) Has been reassembled. However, these materials exhibit poor capacitance due to the low conductivity of the transition metal compounds and poor cycling stability of the conductive polymers. Therefore, it is necessary to search for a new high-performance electrode material to further improve the electrochemical performance of the supercapacitor.
In recent years, binary transition metal oxides (e.g., NiCo)2O4) And sulfides (e.g. sodium sulfide)NiCo2S4、ZnCo2S4) Great interest has been raised in the field of energy storage due to their multiple redox reactions and higher capacitance relative to single-component oxides/sulfides. In particular like MCo2S4Binary transition metal sulfides such as (M ═ Cu, Zn, Ni) can deliver higher electrochemical capacitance due to their high conductivity and superior electrochemical performance. For example, NiCo2S4Is NiCo2O4About 100 times higher, even 4 orders of magnitude higher than the conductivity of nickel or cobalt oxides. Thus, MCo2S4A structural high-performance electrode material with great potential. Recently, FeCo2S4Is reported as being specific to NiCo2O4Better quasi-capacitive materials because of the valence of Fe2+Shows higher electrochemical activity in oxidation-reduction reaction. Despite the many advantages of binary transition metal sulfides, their conductivity and low rate performance in rapid charge and discharge still limit their potential applications. Due to the FeCo base2S4Since there are few reports on the development of pseudo-capacitive electrodes, FeCo having a novel structure and excellent capacitance properties has been sought2S4Electrodes are becoming increasingly necessary.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a Fe-Co-S nanosheet material, and a preparation method and application thereof. The Fe-Co-S nanosheet material has a porous nanostructure with a high effective specific surface area, can provide more electrochemical active sites and a rapid ion transportation way, is simple in preparation method and environment-friendly, greatly shortens the synthesis time, and facilitates large-scale production of the Fe-Co-S nanosheet material.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a preparation method of a Fe-Co-S nanosheet material, which comprises the following steps:
s1: dissolving soluble cobalt salt, soluble ferric salt, urea and ammonium fluoride in water, stirring uniformly, adding thiourea, and carrying out hydrothermal reaction;
s2: and after the hydrothermal reaction is finished, cooling, centrifuging, washing and drying to obtain the Fe-Co-S nanosheet material.
Preferably, the soluble cobalt salt is cobalt nitrate, and the soluble iron salt is ferric nitrate.
Preferably, the mol ratio of the soluble cobalt salt, the soluble iron salt, the ammonium fluoride, the urea and the thiourea is 2 (0.8-1.2) to (8-10) to (4-6) to (0.5-1).
Preferably, the temperature of the hydrothermal reaction is 120-180 ℃, and the time is 8-24 h.
Preferably, the drying is vacuum drying, and the temperature in the drying process is 60-100 ℃ and the time is 10-24 h.
The invention also provides the Fe-Co-S nanosheet material prepared by the preparation method.
The invention also provides application of the Fe-Co-S nanosheet material, and the composite material is prepared into a working electrode for a super capacitor.
Preferably, 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.
Preferably, the mass ratio of the composite material, the carbon black and the polytetrafluoroethylene is 8 (0.8-1.2) to (0.8-1.2).
Preferably, the drying temperature is 50-70 ℃ and the drying time is 10-24h in the process of preparing the working electrode.
In the process of preparing the Fe-Co-S nanosheet material, in the hydrothermal process, the hydrolysis reaction of urea enables Fe2+And Co2+With OH-The reaction is carried out, so that the transport speed of the ion electrons is accelerated; 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 crystal generates the difference in appearance, and high-concentration NH4+Can promote OH-The growth rate is improved, and crystals can grow along the two-dimensional lattice direction to form two-dimensional nano sheetsFurther stacked to form a nanoflower structure.
Compared with the prior art, the invention has the following characteristics:
(1) the Fe-Co-S nanosheet material is hydrothermally synthesized in one step, has a porous nanostructure with a high effective specific surface area, can provide more electrochemical active sites and a rapid ion transportation way, is simple in preparation method and environment-friendly, greatly shortens the synthesis time, and facilitates large-scale production of the Fe-Co-S nanosheet material.
(2) The working electrode prepared by using the Fe-Co-S nanosheet material has high specific capacitance, high energy density and power density and good electrochemical performance, and can be used in a super capacitor.
Drawings
FIG. 1 is an SEM image at 1 μm of Fe-Co-S nanosheets prepared in example 2;
FIG. 2 is a cyclic voltammogram of the Fe-Co-S nanosheet material prepared in example 2 at different sweep rates;
FIG. 3 is a GCD plot of Fe-Co-S nanosheets made in example 2 at different current densities;
FIG. 4 is a GCD plot at a current density of 1A/g for Fe-Co-S nanosheets made in the comparative examples.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The raw materials used in the examples are commercially available unless otherwise specified.
Comparative example
A preparation method of Fe-Co-S nanosheet material comprises the following steps:
2mmol of Co (NO)3)2·6H2O、0.8mmol Fe(NO3)3·9H2Dissolving O and 4mmol of urea in 40mL of water, magnetically stirring uniformly, adding 0.1g of thiourea, quickly transferring to an 80mL stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out one-step hydrothermal reaction at 120 ℃ for 8 hours; hydrothermal sampleTaking out, cooling, centrifuging, washing, and vacuum drying at 60 deg.C for 12 hr to obtain 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 an oven at the temperature of 60 ℃ for 12 hours to obtain the Fe-Co-S working electrode (marked as FCS-1).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: FCS-1 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1192F/g in 2mol/L KOH solution and at a current density of 1A/g, as shown in FIG. 4.
Example 1
A preparation method of Fe-Co-S nanosheet material comprises the following steps:
2mmol of Co (NO)3)2·6H2O、0.8mmol Fe(NO3)3·9H2O、8mmol NH4F. Dissolving 4mmol of urea in 40mL of water, magnetically stirring uniformly, adding 0.1g of thiourea, quickly transferring to an 80mL stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out one-step hydrothermal reaction at 120 ℃ for 8 hours; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain 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 an oven at the temperature of 60 ℃ for 12 hours to obtain the Fe-Co-S working electrode (marked as FCS-1).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: FCS-1 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 3164F/g in 2mol/L KOH solution and at a current density of 1A/g.
In the process of preparing the Fe-Co-S nanosheet material, thiourea is used as a sulfur source, and the main preparation mechanism is as follows:
H2NCONH2+4H2O→CO3 2-+2NH3·H2O+2H+
NH4F+H2O→NH4 ++F-
NH4 ++H2O→NH3·H2O+H+
CO3 2-+H+→HCO3 -+
Fe3++2Co2++xOH-+yCO3 2-+zHCO3 -→FeCo2(OH)x(CO3)y(HCO3)z
FeCo2(OH)x(CO3)y(HCO3)z+(3-x+z)OH-+(1.5-y-z)CO3 2-→
FeCo2(OH)3(CO3)1.5+zH2O
example 2
A preparation method of Fe-Co-S nanosheet material comprises the following steps:
2mmol of Co (NO)3)2·6H2O、1mmol Fe(NO3)3·9H2O、8mmol NH4F. Dissolving 4mmol of urea in 40mL of water, magnetically stirring uniformly, adding 0.5g of thiourea, quickly transferring to an 80mL stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out one-step hydrothermal reaction at 120 ℃ for 8 hours; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain 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, and pressing the mixture on a foam nickel sheet (1cm multiplied by 1)cm) and dried in an oven at 60 ℃ for 12 hours to obtain an Fe-Co-S working electrode (denoted FCS-2).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: FCS-2 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. Under the condition of 2mol/L KOH solution and the current density of 1A/g, the specific capacitance of the composite material reaches 2550F/g.
FIG. 1 is an SEM image of the prepared Fe-Co-S nanosheet at a thickness of 1 μm, and as can be seen from FIG. 1, a three-dimensional (3D) nanoflower structure can be easily obtained after the Fe-Co-S is subjected to vulcanization treatment.
FIG. 2 is a CV diagram of the prepared Fe-Co-S nanosheets at different sweep rates, wherein the sweep rates are 5, 10, 15, 20 and 40mV/S respectively. As can be seen from the figure, at a voltage range of 0-0.6V, there are a pair of symmetrical redox peaks, and as the sweep rate increases, the oxidation peak and the reduction peak move to the right and left, respectively. The phenomenon shows that the prepared Fe-Co-S nanosheet material has good reversibility and stability.
FIG. 3 is a GCD diagram of the prepared Fe-Co-S nanosheets under different current densities.
Example 3
A preparation method of Fe-Co-S nanosheet material comprises the following steps:
2mmol of Co (NO)3)2·6H2O、1mmol Fe(NO3)3·9H2O、8mmol NH4F. Dissolving 4mmol of urea in 40mL of water, magnetically stirring uniformly, adding 0.5g of thiourea, quickly transferring to an 80mL stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out one-step hydrothermal reaction at 140 ℃ for 8 hours; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain 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, and pressing the mixture on a foam nickel sheet (1cm multiplied by 1cm)And drying the mixture in an oven at 60 ℃ for 12 hours to obtain the Fe-Co-S working electrode (denoted by FCS-3).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: FCS-3 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1550F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 4
A preparation method of Fe-Co-S nanosheet material comprises the following steps:
2mmol of Co (NO)3)2·6H2O，1mmol Fe(NO3)3·9H2O，8mmol NH4Dissolving 4mmol of urea in 40mL of water, magnetically stirring uniformly, adding 0.5g of thiourea, quickly transferring into an 80mL stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out one-step hydrothermal reaction at 180 ℃ for 8 hours; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain 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 an oven at the temperature of 60 ℃ for 12 hours to obtain the Fe-Co-S working electrode (marked as FCS-4).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: FCS-4 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1750F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 5
A preparation method of Fe-Co-S nanosheet material comprises the following steps:
2mmol of Co (NO)3)2·6H2O、1mmol Fe(NO3)3·9H2O、8mmol NH4F. Dissolving 4mmol of urea in 40mL of water, magnetically stirring uniformly, adding 0.5g of thiourea, quickly transferring to an 80mL stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out one-step hydrothermal reaction at 180 ℃ for 12 hours; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain 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 an oven at the temperature of 60 ℃ for 12 hours to obtain the Fe-Co-S working electrode (marked as FCS-5).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: FCS-5 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1690F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 6
A preparation method of Fe-Co-S nanosheet material comprises the following steps:
2mmol of Co (NO)3)2·6H2O、1mmol Fe(NO3)3·9H2O、8mmol NH4F. Dissolving 4mmol of urea in 40mL of water, magnetically stirring uniformly, adding 0.5g of thiourea, quickly transferring to an 80mL stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out one-step hydrothermal reaction at 180 ℃ for 24 hours; and taking out the hydrothermal sample, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain powder. Grinding the active material, mixing with carbon black and polytetrafluoroethylene uniformly according to the mass ratio of 8:1:1, pressing on a foam nickel sheet (1cm multiplied by 1cm), and baking at 60 DEG CAnd drying in a box for 12h to obtain the Fe-Co-S working electrode (denoted by FCS-6).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: FCS-6 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 2170F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 7
This example is substantially the same as example 1 except that the mass of thiourea was 0.3g in this example.
Example 8
This example is essentially the same as example 1, except that in this example, the molar ratio of soluble cobalt salt, soluble iron salt, ammonium fluoride to urea is 2:1.2:10: 6.
Example 9
This example is essentially the same as example 1, except that in this example, the molar ratio of soluble cobalt salt, soluble iron salt, ammonium fluoride to urea is 2:1:9: 5.
Example 10
The present embodiment is substantially the same as embodiment 1, except that in the present embodiment, the drying temperature during the preparation process of the Fe-Co-S nanosheet material is 80 ℃, and the time is 24 h.
Example 11
The present embodiment is substantially the same as embodiment 1, except that in the present embodiment, the drying temperature during the preparation process of the Fe-Co-S nanosheet material is 100 ℃, and the time is 10 h.
Example 12
This example is substantially the same as example 1, except that in this example, the mass ratio of the composite material, carbon black and polytetrafluoroethylene in the working electrode was 8:1.2: 0.8.
Example 13
This example is substantially the same as example 1, except that in this example, the mass ratio of the composite material, carbon black and polytetrafluoroethylene in the working electrode was 8:0.8: 1.2.
Example 14
This example is substantially the same as example 1, except that in this example, the excess drying temperature was 50 ℃ and the time was 24 hours during the working electrode preparation process.
Example 15
This example is substantially the same as example 1, except that in this example, the excess drying temperature was 70 ℃ and the time was 10 hours during the working electrode preparation process.
The embodiments described above are intended to facilitate the 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 (9)
1. A preparation method of Fe-Co-S nanosheet material is characterized by comprising the following steps:
s1: dissolving soluble cobalt salt, soluble ferric salt, urea and ammonium fluoride in water, stirring uniformly, adding thiourea, and carrying out hydrothermal reaction;
s2: and after the hydrothermal reaction is finished, cooling, centrifuging, washing and drying to obtain the Fe-Co-S nanosheet material.
2. The method of claim 1, wherein the soluble cobalt salt is cobalt nitrate and the soluble iron salt is ferric nitrate.
3. The method for preparing Fe-Co-S nanosheet material according to claim 1 or 2, wherein the molar ratio of the soluble cobalt salt, the soluble iron salt, the ammonium fluoride, the urea and the thiourea is 2 (0.8-1.2): 8-10): 4-6: 0.5-1.
4. The method for preparing Fe-Co-S nanosheet material as recited in claim 1, wherein the hydrothermal reaction is carried out at a temperature of 120 ℃ and 180 ℃ for a period of 8-24 hours.
5. The method for preparing Fe-Co-S nanosheet material according to claim 1, wherein the drying is vacuum drying, and wherein the drying is carried out at a temperature of 60-100 ℃ for a time of 10-24 hours.
6. The Fe-Co-S nanosheet material prepared by the preparation method according to any one of claims 1 to 5.
7. The use of the Fe-Co-S nanosheet material of claim 6, wherein the composite is prepared as a working electrode for use in a supercapacitor.
8. The use of Fe-Co-S nanosheet material as recited in claim 7, wherein the 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 Fe-Co-S nanosheet material as recited in claim 8, wherein the weight ratio of the composite material, carbon black and polytetrafluoroethylene is 8 (0.8-1.2) to (0.8-1.2).
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