CN114664573A - Phosphorus-doped nickel-cobalt-sulfur composite electrode material and preparation method and application thereof - Google Patents
Phosphorus-doped nickel-cobalt-sulfur composite electrode material and preparation method and application thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000000243 solution Substances 0.000 claims abstract description 46
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 239000006260 foam Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 11
- 238000004146 energy storage Methods 0.000 abstract description 7
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- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- 238000007599 discharging Methods 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
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- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 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
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- 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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- 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
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Abstract
The invention relates to an energy storage material, in particular to a phosphorus-doped nickel-cobalt-sulfur composite electrode material and a preparation method and application thereof, and the preparation method comprises the following steps: s1: adding a nickel source, a cobalt source and a sulfur source into the mixed solution to obtain a precursor solution; s2: immersing the pretreated foam nickel into the precursor solution for hydrothermal reaction, cooling to natural room temperature, washing and drying to obtain NiCo2S4@ NF composite electrode materials; s3: NiCo by phosphorus source2S4And (3) phosphating the @ NF composite electrode material, cooling to natural room temperature, washing and drying to obtain the phosphorus-doped nickel-cobalt-sulfur composite electrode material. Compared with the prior art, the invention improves the electrochemical performance of the material by doping phosphorus element, and the specific surface area of the material can be increased by taking the foamed nickel as the substrateThe electrode material prepared by the synthesis method has excellent performance and simple method, and can realize large-scale industrial application.
Description
Technical Field
The invention belongs to the field of nano materials and electrochemistry, and particularly relates to a phosphorus-doped nickel-cobalt-sulfur composite electrode material as well as a preparation method and application thereof.
Background
With the mass combustion of fossil fuels, the problem of energy shortage and the problem of environmental pollution have become more serious, and in order to solve these problems, the search for new renewable energy sources is urgent. When looking for new energy, the energy storage problem has also received extensive attention, and neotype energy storage device can effectively improve the utilization ratio of the energy. Energy storage devices in the market at present mainly comprise lithium ion batteries and secondary lead storage batteries, however, the lithium ion batteries and the lead storage batteries have a large safety problem. The super capacitor is used as a novel energy storage device between a traditional capacitor and a secondary battery, has the advantages of high charging and discharging speed (the charging time is generally between dozens of seconds and hundreds of seconds) of the traditional capacitor, high power density (the power density of the super capacitor can reach hundreds of times and more than that of a lithium ion battery) and the like, also has excellent energy storage characteristics of the secondary battery, and has the greatest advantages of greenness, safety and no pollution. Currently, a super capacitor is one of effective substitutes for lithium ion batteries and secondary batteries, and has a large potential in the aspect of energy storage. However, the low energy density of the super capacitor itself limits the industrial mass production thereof.
The electrode material is used as the core composition of the super capacitor, plays a decisive role in the performance of the super capacitor, and the transition metal compound is researched by a large number of researchers as an excellent electrode material. Nickel cobalt sulfur compounds stand out from numerous transition metal compounds because of the large storage capacity and low cost of nickel and cobalt elements, and the better conductivity of cobalt nickel sulfur over nickel cobalt oxide and cobalt nickel hydroxide. Because the nickel-cobalt-sulfur has semiconductor properties, the application of the nickel-cobalt-sulfur is limited due to the large band gap, poor hydrophilicity and few active sites of the nickel-cobalt-sulfur.
Disclosure of Invention
The invention aims to solve the problems and provide a phosphorus-doped nickel-cobalt-sulfur composite electrode material and a preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme:
the invention discloses a preparation method of a phosphorus-doped nickel-cobalt-sulfur composite electrode material, which comprises the following steps:
s1: adding a nickel source, a cobalt source and a sulfur source into the mixed solution to obtain a precursor solution;
s2: carrying out hydrothermal reaction on the precursor solution obtained in the step S1 and foamed nickel, cooling, washing and drying to obtain NiCo2S4@ NF composite electrode materials;
s3: the NiCo obtained in the step S2 is mixed with a phosphorus source2S4The @ NF composite electrode material is phosphorized, cooled, washed and dried to obtain the phosphorus-doped nickel cobalt sulfur (P-NiCo)2S4@ NF) composite electrode material.
Preferably, the ratio of the nickel source, the cobalt source, the sulfur source and the phosphorus source is 0.8-1.2mmol:1.6-2.4mmol:3.2-4.8mmol:3.2-5.0 mmol. Still more preferably, wherein the ratio of the nickel source, the cobalt source and the sulfur source is 1mmol:2mmol:4 mmol.
Preferably, the nickel source is selected to be Ni (NO)3)2·6H2O; the cobalt source is selected to be Co (NO)3)2·6H2O; the sulfur source is selected from CS (NH)2)2(ii) a The phosphorus source is Na2HPO2·H2O。
Preferably, the mixed solution comprises ethylene glycol and deionized water, wherein the usage amount of the ethylene glycol and the deionized water is 30-50mL respectively, and the volume ratio is 1: 1.
Preferably, the size of the foamed nickel is (10-20) mm x (2-6) mm x l mm.
Preferably, the temperature of the hydrothermal reaction is 110-130 ℃, and the time is 24-48 h.
Preferably, the washing is the cross washing of absolute ethyl alcohol and deionized water, and the times are not less than 3 times and not more than 6 times; the drying is vacuum drying at 60 ℃ for 6-12 h.
Preferably, the phosphorization is carried out in a tubular furnace at the temperature of 300-400 ℃ and the heating rate of 2-5 ℃ for min-1The heat preservation time is 2-6 h.
Preferably, the phosphorization is carried out in a tubular furnace at the temperature of 300 ℃ and the heating rate of 2 ℃ for min-1Keeping the temperature for 4 hours, cooling to room temperature, and alternately cleaning by absolute ethyl alcohol and deionized water, wherein the drying is vacuum drying at 60 ℃ for 6-12 hours.
Preferably, the nickel source, the cobalt source and the sulfur source are sufficiently dissolved in the mixed solution in step S1, and are magnetically stirred for 50-80 min.
Preferably, the pretreated foamed nickel is the foamed nickel, after being cut, the foamed nickel is respectively washed in acetone solution, absolute ethyl alcohol solution and deionized water for 15min, and dried for 12-24h under the condition of 60-90 ℃ in a vacuum drying oven.
The invention discloses a phosphorus-doped nickel-cobalt-sulfur composite electrode material, which is prepared by any one of the preparation methods.
The invention discloses an application of the phosphorus-doped nickel-cobalt-sulfur composite electrode material in a super capacitor.
The proportion of nickel, cobalt and sulfur is controlled in the invention so as to ensure that the nickel, cobalt and sulfur are better and uniformly loaded on the surface of the foamed nickel in the hydrothermal reaction, and the proportion is too low, so that the loading is not enough to be completely carriedWrapping a foamed nickel substrate; too high a ratio may cause an excessive load, thereby degrading electrochemical performance, and the load may be controlled according to the concentration of the precursor solution. The doping of the phosphorus element can promote P-NiCo2S4The service life and the circulation stability of the @ NF electrode material can effectively improve the electron transmission capability and enable the @ NF electrode material to store more energy; compared with non-metal elements such as nitrogen, sulfur, boron and the like, the phosphorus element has larger atomic radius, can promote the distribution of charge density and form a hydrophilic polar surface, thereby promoting the rapid formation of stable pseudocapacitance in the process of ion charging and discharging; meanwhile, the doping of the phosphorus-containing functional group can provide a Faraday active site for the pseudocapacitance, so that the electrochemical performance is further improved.
Compared with the prior art, the invention has the following beneficial effects:
1. the electrode material prepared by the invention has the advantages of simple method, low raw material price, higher specific capacitance and good application prospect in the electrochemical field.
2. According to the invention, the precursor is prepared by adopting a one-step hydrothermal method, the process is further optimized, the time cost is saved, the phosphorus element can be doped by calcining in a tubular furnace, and the electrochemical performance of the material is greatly improved. The electrochemical performance of the material is improved by doping phosphorus, the specific surface area of the material can be increased by taking the foamed nickel as a substrate, and the electrode material prepared by the synthesis method has excellent performance and simple method, and can realize large-scale industrial application.
3. The electrode material prepared by the method has the advantages of simple process, low price and the like. At 0.5A g-1In the case of (2), the capacitance is 2388F g-1Providing a P-NiCo2S4The preparation method of the @ NF electrode material has better experimental data support.
Drawings
FIG. 1 is a P-NiCo representation of example 22S4@ NF electrode Material and NiCo prepared in comparative example 22S4@ NF electrode material at 20mV s-1A comparison of lower cyclic voltammograms;
FIG. 2 is a schematic representation of the P-NiCo example 22S4@ NF electrode Material and NiCo prepared in comparative example 22S4Comparative plot of constant current charge and discharge of @ NF electrode material;
FIG. 3 is a schematic representation of the P-NiCo example 22S4@ NF electrode Material and NiCo prepared in comparative example 22S4Comparative electrochemical impedance spectroscopy of @ NF electrode materials.
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.
In each of the following examples, except that the test used in the present invention was Chenghua electrochemical workstation, model number CHI 660E; the rest is NF and Ni (NO)3)2·6H2O、Co(NO3)2·6H2O and CS (NH)2)2And the like, and if not specifically mentioned, indicates that the raw materials or the treatment techniques are all conventional commercial products or conventional treatment techniques in the field.
Example 1
P-NiCo2S4The preparation method of the @ NF electrode material comprises the following steps:
s1: 0.2908g Ni (NO) is weighed3)2·6H2O and 0.5820g Co (NO)3)2·6H2O, transferring into a 100mL beaker; weighing 45mL of deionized water and 45mL of ethylene glycol, uniformly mixing, transferring into a 100mL beaker, placing the prepared solution on a magnetic stirrer, and starting stirring; after stirring well, 0.3045g of CS (NH) was weighed2)2Adding CS (NH)2)2Adding the prepared solution, and magnetically stirring for 1h to obtain a precursor solution A. And transferring the treated nickel foam and the prepared solution into a reaction kettle, and carrying out one-step hydrothermal reaction at the temperature of 120 ℃ for 24 hours. Taking out the sample after hydrothermal treatment, cooling to room temperature, washing, and vacuum drying for 6h to obtain NiCo2S4@ NF electrode material.
S2: weigh 0.5g Na2HPO2·H2O and mixing it with NiCo obtained from S12S4The material of @ NF electrode is transferred into a tubular furnace at the same time, the set temperature is 300 ℃, and the temperature rise time is set to be 2 ℃ s-1Setting the heat preservation time to be 4h, then cooling to room temperature, washing and vacuum drying the sample for 6h to obtain the P-NiCo2S4@ NF electrode material.
P-NiCo prepared from S22S4The @ NF electrode material is used as a working electrode, Ag/AgCl is used as a reference electrode, and a platinum wire is used as a counter electrode.
The Chenghua CHI660E electrochemical workstation adopts different cyclic voltammetry, constant current charge-discharge and electrochemical impedance spectroscopy methods, adopts a three-electrode test system, connects a working electrode, a counter electrode and a reference electrode to the electrochemical workstation, and performs electrochemical measurement at 3mol L-1The electrochemical performance of the electrode material was measured in KOH solution. The electrode material is 0.5A g-1The specific capacitance reaches 2000F g-1。
Example 2
P-NiCo2S4The preparation method of the @ NF electrode material comprises the following steps:
s1: 0.2908g Ni (NO) is weighed3)2·6H2O and 0.5820g Co (NO)3)2·6H2O, transferring the mixture into a 100mL beaker; weighing 40mL of deionized water and 40mL of ethylene glycol, uniformly mixing, transferring into a 100mL beaker, putting the prepared solution on a magnetic stirrer, and starting stirring; after stirring well, 0.6090g of CS (NH) were weighed2)2Adding CS (NH)2)2Adding the prepared solution, and magnetically stirring for 1h to obtain a precursor solution A. And transferring the treated nickel foam and the prepared solution into a reaction kettle, and carrying out one-step hydrothermal reaction at the temperature of 120 ℃ for 24 hours. Taking out the sample after hydrothermal treatment, cooling to room temperature, washing, and vacuum drying for 6h to obtain NiCo2S4@ NF electrode material.
S2: weigh 0.48g of Na2HPO2·H2O, and mixing it with NiCo2S4@ NF electrode materialSimultaneously transferring the mixture into a tube furnace, setting the temperature to be 300 ℃, and setting the temperature rise time to be 2 ℃ s-1Setting the heat preservation time to be 4h, then cooling to room temperature, washing and vacuum drying the sample for 6h to obtain the P-NiCo2S4@ NF electrode material.
The prepared P-NiCo2S4The @ NF electrode material is used as a working electrode, Ag/AgCl is used as a reference electrode, and a platinum wire is used as a counter electrode.
The Chenghua CHI660E electrochemical workstation adopts different cyclic voltammetry, constant current charge-discharge and electrochemical impedance spectroscopy methods, adopts a three-electrode test system, connects a working electrode, a counter electrode and a reference electrode to the electrochemical workstation, and performs electrochemical measurement at 3mol L-1The electrochemical performance of the electrode material was measured in KOH solution. The electrode material is 0.5A g-1Next, the specific capacitance reaches 2388F g-1。
Example 3
P-NiCo2S4The preparation method of the @ NF electrode material comprises the following steps:
s1: 0.2908g Ni (NO) is weighed3)2·6H2O and 0.5820g Co (NO)3)2·6H2O, transferring the mixture into a 100mL beaker; weighing 35mL of deionized water and 35mL of ethylene glycol, uniformly mixing, transferring into a 100mL beaker, placing the prepared solution on a magnetic stirrer, and starting stirring; after stirring well, 0.6090g of CS (NH) were weighed2)2Adding CS (NH)2)2Adding the prepared solution, and magnetically stirring for 1h to obtain a precursor solution A. And transferring the treated nickel foam and the prepared solution into a reaction kettle, and carrying out one-step hydrothermal reaction at the temperature of 120 ℃ for 24 hours. Taking out the sample after hydrothermal treatment, cooling to room temperature, washing, and vacuum drying for 6h to obtain NiCo2S4@ NF electrode material.
S2: 0.46g of Na was weighed2HPO2·H2O, and mixing it with NiCo2S4The material of @ NF electrode is transferred into a tubular furnace at the same time, the set temperature is 300 ℃, and the temperature rise time is set to be 2 ℃ s-1The holding time is set to 4h, and then the mixture is cooled to the room temperature, and the sample is obtainedWashing and vacuum drying the product for 6h to obtain the P-NiCo2S4@ NF electrode material.
The P-NiCo prepared in the step S22S4The @ NF electrode material is used as a working electrode, Ag/AgCl is used as a reference electrode, and a platinum wire is used as a counter electrode.
Chenhua CHI660E electrochemical workstation adopts different cyclic voltammetry, constant current charge and discharge and electrochemical impedance spectroscopy methods, adopts three-electrode test system, connects working electrode, counter electrode and reference electrode to the electrochemical workstation, and processes at 3mol L-1The electrochemical performance of the electrode material was measured in KOH solution. The electrode material is 0.5A g-1The specific capacitance reaches 2200F g-1。
Example 4
P-NiCo2S4The preparation method of the @ NF electrode material comprises the following steps:
s1: 0.2908g Ni (NO) is weighed3)2·6H2O and 0.5820g Co (NO)3)2·6H2O, transferring the mixture into a 100mL beaker; weighing 30mL of deionized water and 30mL of ethylene glycol, uniformly mixing, transferring into a 100mL beaker, putting the prepared solution on a magnetic stirrer, and starting stirring; after stirring well, 0.6090g of CS (NH) were weighed2)2Adding CS (NH)2)2Adding the prepared solution, and magnetically stirring for 1h to obtain a precursor solution A. And transferring the treated nickel foam and the prepared solution into a reaction kettle, and carrying out one-step hydrothermal reaction at the temperature of 120 ℃ for 24 hours. Taking out the sample after hydrothermal treatment, cooling to room temperature, washing, and vacuum drying for 6h to obtain NiCo2S4@ NF electrode material.
S2: weigh 0.48g of Na2HPO2·H2O, and mixing it with NiCo2S4The material of @ NF electrode is transferred into a tubular furnace at the same time, the set temperature is 300 ℃, and the temperature rise time is set to be 2 ℃ s-1Setting the heat preservation time to be 4h, then cooling to room temperature, washing and vacuum drying the sample for 6h to obtain the P-NiCo2S4@ NF electrode material.
Mixing the aboveThe P-NiCo is obtained2S4The @ NF electrode material is used as a working electrode, Ag/AgCl is used as a reference electrode, and a platinum wire is used as a counter electrode.
The Chenghua CHI660E electrochemical workstation adopts different cyclic voltammetry, constant current charge-discharge and electrochemical impedance spectroscopy methods, adopts a three-electrode test system, connects a working electrode, a counter electrode and a reference electrode to the electrochemical workstation, and performs electrochemical measurement at 3mol L-1The electrochemical performance of the electrode material was measured in KOH solution. The electrode material is 0.5A g-1Next, the specific capacitance reached 2100F g-1。
Comparative example 1
NiCo2S4The preparation method of the @ NF electrode material comprises the following steps:
0.2908g Ni (NO) is weighed3)2·6H2O and 0.5820g Co (NO)3)2·6H2O, transferring the mixture into a 100mL beaker; weighing 45mL of deionized water and 45mL of ethylene glycol, uniformly mixing, transferring into a 100mL beaker, placing the prepared solution on a magnetic stirrer, and starting stirring; after stirring well, 0.6090g of CS (NH) were weighed2)2Mixing CS (NH)2)2Adding the prepared solution, and magnetically stirring for 1h to obtain a solution A. And transferring the treated nickel foam and the prepared solution into a reaction kettle, and carrying out one-step hydrothermal reaction at the temperature of 120 ℃ for 24 hours. Taking out the sample after hydrothermal treatment, cooling to room temperature, washing, and vacuum drying for 6h to obtain NiCo2S4@ NF electrode material. The electrode material is 0.5Ag-1The specific capacitance of the lower material was 1500F g-1。
Comparative example 2
NiCo2S4The preparation method of the @ NF electrode material comprises the following steps:
0.2908g Ni (NO) is weighed3)2·6H2O and 0.5820g Co (NO)3)2·6H2O, transferring the mixture into a 100mL beaker; weighing 40mL of deionized water and 40mL of ethylene glycol, uniformly mixing, transferring into a 100mL beaker, putting the prepared solution on a magnetic stirrer, and starting stirring; after stirring well, 0.6090g were weighed CS(NH2)2Adding CS (NH)2)2Adding the prepared solution, and magnetically stirring for 1h to obtain a solution A. And transferring the treated foamed nickel and the prepared solution into a reaction kettle, and carrying out one-step hydrothermal reaction at the temperature of 120 ℃ for 24 hours. Taking out the sample after hydrothermal treatment, cooling to room temperature, washing, and vacuum drying for 6h to obtain NiCo2S4@ NF electrode material. The electrode material is 0.5Ag-1The specific capacitance is 1568F g-1。
FIG. 1 is a P-NiCo representation of example 22S4@ NF electrode Material and NiCo prepared in comparative example 22S4@ NF electrode material at 20mV s-1Comparative plot of lower cyclic voltammograms. P-NiCo obtainable from FIG. 12S4Compared with NiCo, the @ NF composite electrode material2S4@ NF composite electrode material at 20mV s-1The method has better cycle stability at the scanning speed.
FIG. 2 shows P-NiCo in example 22S4@ NF electrode Material and NiCo prepared in comparative example 22S4Comparative plot of galvanostatic charging and discharging of @ NF electrode materials. As can be seen from FIG. 2, P-NiCo was produced2S4Compared with NiCo, the @ NF composite electrode material2S4The oxidation-reduction reaction of the @ NF composite electrode material has better reversibility.
FIG. 3 is a schematic representation of the P-NiCo example 22S4@ NF electrode Material and NiCo prepared in comparative example 22S4Comparative electrochemical impedance spectroscopy of @ NF electrode materials. It can be seen from FIG. 3 that P-NiCo is produced2S4Compared with NiCo, the @ NF composite electrode material2S4The @ NF composite electrode material has smaller reactance and is more suitable for being used as the electrode material of the supercapacitor.
Comparative example 3
NiCo2S4The preparation method of the @ NF electrode material comprises the following steps:
0.2908g Ni (NO) is weighed3)2·6H2O and 0.5820g Co (NO)3)2·6H2O, transferring the mixture into a 100mL beaker; weigh 35mL toAfter the ionized water and 35mL of glycol are uniformly mixed, moving the mixture into a 100mL beaker, putting the prepared solution on a magnetic stirrer, and starting stirring; after stirring well, 0.6090g of CS (NH) were weighed2)2Mixing CS (NH)2)2Adding the prepared solution, and magnetically stirring for 1h to obtain a solution A. And transferring the treated nickel foam and the prepared solution into a reaction kettle, and carrying out one-step hydrothermal reaction at the temperature of 120 ℃ for 24 hours. Taking out the sample after hydrothermal treatment, cooling to room temperature, washing, and vacuum drying for 6h to obtain NiCo2S4@ NF electrode material. The material is 0.5Ag-1The specific capacitance is 1560F g-1。
Comparative example 4
NiCo2S4The preparation method of the @ NF electrode material comprises the following steps:
0.2908g Ni (NO) is weighed3)2·6H2O and 0.5820g Co (NO)3)2·6H2O, transferring the mixture into a 100mL beaker; weighing 30mL of deionized water and 30mL of ethylene glycol, uniformly mixing, transferring into a 100mL beaker, putting the prepared solution on a magnetic stirrer, and starting stirring; after stirring well, 0.6090g of CS (NH) were weighed2)2Adding CS (NH)2)2Adding the prepared solution, and magnetically stirring for 1h to obtain a solution A. And transferring the treated nickel foam and the prepared solution into a reaction kettle, and carrying out one-step hydrothermal reaction at the temperature of 120 ℃ for 24 hours. Taking out the sample after hydrothermal treatment, cooling to room temperature, washing, and vacuum drying for 6h to obtain NiCo2S4@ NF electrode material. The material is 0.5Ag-1The specific capacitance is 1530F g-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 (8)
1. A preparation method of a phosphorus-doped nickel-cobalt-sulfur composite electrode material is characterized by comprising the following steps:
s1: adding a nickel source, a cobalt source and a sulfur source into the mixed solution to obtain a precursor solution;
s2: immersing the pretreated nickel foam into the precursor solution obtained in S1 for hydrothermal reaction, cooling to natural room temperature, washing and drying to obtain NiCo2S4@ NF composite electrode materials;
s3: the NiCo obtained in the step S2 is added by a phosphorus source2S4And (2) phosphatizing the @ NF composite electrode material, cooling to natural room temperature, washing and drying to obtain the phosphorus-doped nickel-cobalt-sulfur composite electrode material.
2. The preparation method of the phosphorus-doped nickel-cobalt-sulfur composite electrode material as claimed in claim 1, wherein the ratio of the nickel source to the cobalt source to the sulfur source to the phosphorus source is 0.8-1.2mmol:1.6-2.4mmol:3.2-4.8mmol:3.2-5.0 mmol.
3. The method as claimed in claim 2, wherein the nickel source is selected from Ni (NO)3)2·6H2O; the cobalt source is selected from Co (NO)3)2·6H2O; the sulfur source is selected from CS (NH)2)2(ii) a The phosphorus source is selected from Na2HPO2·H2O。
4. The preparation method of the phosphorus-doped nickel-cobalt-sulfur composite electrode material as claimed in claim 1, wherein the mixed solution comprises ethylene glycol and deionized water, the usage amount of the ethylene glycol and the deionized water is 30-50mL respectively, and the volume ratio is 1: 1.
5. The method for preparing a phosphorus-doped nickel-cobalt-sulfur composite electrode material as claimed in claim 1, wherein the hydrothermal reaction is carried out at a temperature of 110-130 ℃ for 24-48 h.
6. The method for preparing a phosphorus-doped nickel-cobalt-sulfur composite electrode material as claimed in claim 1, wherein the phosphorization is carried out in a tubular furnace at a temperature of 300 ℃ and 400 ℃ and a heating rate of 2-5 ℃ for min-1The heat preservation time is 2-6 h.
7. A phosphorus-doped nickel-cobalt-sulfur composite electrode material, characterized by being prepared by the preparation method according to any one of claims 1 to 6.
8. Use of the phosphorus doped nickel cobalt sulfur composite electrode material of claim 7 in a supercapacitor.
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