CN114551119A - High-performance supercapacitor electrode material and preparation method thereof - Google Patents
High-performance supercapacitor electrode material and preparation method thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 139
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 67
- 239000006260 foam Substances 0.000 claims abstract description 66
- 239000002070 nanowire Substances 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 239000003990 capacitor Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000002243 precursor Substances 0.000 claims description 39
- 238000001816 cooling Methods 0.000 claims description 34
- 239000003575 carbonaceous material Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 229920001568 phenolic resin Polymers 0.000 claims description 23
- 239000005011 phenolic resin Substances 0.000 claims description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 19
- 238000001291 vacuum drying Methods 0.000 claims description 18
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 13
- 238000010335 hydrothermal treatment Methods 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000008098 formaldehyde solution Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 150000002815 nickel Chemical class 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 7
- 150000002696 manganese Chemical class 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- MBUJIFHANTWAKB-UHFFFAOYSA-N [S-2].[Mn+2].[Co+2].[Ni+2].[S-2].[S-2] Chemical compound [S-2].[Mn+2].[Co+2].[Ni+2].[S-2].[S-2] MBUJIFHANTWAKB-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 230000005540 biological transmission Effects 0.000 abstract description 14
- 239000000758 substrate Substances 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 2
- 238000004873 anchoring Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 37
- 239000003792 electrolyte Substances 0.000 description 34
- 238000009792 diffusion process Methods 0.000 description 21
- 238000002484 cyclic voltammetry Methods 0.000 description 17
- 239000011149 active material Substances 0.000 description 15
- 239000002159 nanocrystal Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 229920003987 resole Polymers 0.000 description 10
- 238000011056 performance test Methods 0.000 description 9
- 238000007600 charging Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 7
- 239000002149 hierarchical pore Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 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
- H01G11/84—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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- 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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- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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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
- H01G11/30—Electrodes characterised by their material
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention aims to provide a high-performance supercapacitor electrode material and a preparation method thereof by comprehensively utilizing two strategies of nickel foam substrate anchoring and hierarchical porous carbon coating aiming at the defects of small specific surface area, poor conductivity, poor structural stability and the like of the conventional supercapacitor electrode material. The prepared hierarchical porous carbon coating CoNiMn-S nanowire material loaded on nickel foam shows high specific capacitance, good rate performance, low transmission resistance and excellent circulation stability when being used as an electrode material of a super capacitor, and has huge application potential in the field of super capacitors.
Description
Technical Field
The invention relates to the field of electrode materials of supercapacitors.
Background
The super capacitor is a novel green energy storage device, has the advantages of high charging and discharging speed, high efficiency, long cycle life, wide use temperature range, good safety, no pollution to the environment and the like, and has wide application prospect in the aspects of fuel cell vehicles, hybrid electric vehicles, buses, low-temperature starting of vehicles, solar system power storage devices, high-power rapid charging power supplies and the like.
The electrode material is a key factor in determining the performance of the supercapacitor. The existing electrode material of the super capacitor has the defects of small specific surface area, poor conductivity, poor structural stability and the like, and the performance of the electrode material needs to be improved.
Disclosure of Invention
The invention aims to provide a preparation method of a high-performance supercapacitor electrode material, which is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of oligomeric phenolic resin: dissolving phenol and formaldehyde in a sodium hydroxide solution, heating and stirring to prepare oligomeric phenolic resin;
(2) preparing a hierarchical porous carbon material: adding template agents P123 and F127 into the oligomeric phenolic resin prepared in the step (1), stirring to react, cooling to room temperature, transferring the obtained product into a hydrothermal kettle, separating a solid product after the hydrothermal reaction is finished and the cooling to room temperature, roasting the solid product under the protection of inert gas, cooling, and grinding into powder to obtain the hierarchical porous carbon material;
(3) preparing a precursor: mixing cobalt salt, nickel salt, manganese salt, urea and NH4F is added into deionized water to prepare a CoNiMn precursor;
transferring the CoNiMn precursor into a hydrothermal kettle, adding nickel foam, fully reacting, and cleaning a filtered product to obtain the CoNiMn precursor loaded on a nickel foam carrier;
(4) preparing a hierarchical porous carbon coating CoNiMn-S nanowire loaded on nickel foam: adding the hierarchical porous carbon material prepared in the step (2) into Na2S·9H2Adding the CoNiMn precursor loaded on the nickel foam carrier prepared in the step (3) into the O aqueous solution, cooling to room temperature after the mixture is subjected to hydrothermal reaction, and filtering, washing and drying the product to obtain the hierarchical porous carbon coating cobalt nickel manganese loaded on the nickel foamSulfide nanowire composite electrode material (CoNiMn-S @ HPC).
Further, the amount of the sodium hydroxide solution used in the step (1) is 4-6 ml of 0.5M sodium hydroxide solution per 1g of phenol;
further, the dosage of the formaldehyde solution in the step (1) is 2.5-4.5 ml of formaldehyde solution with the concentration of 37-40% used for every 1g of phenol;
further, when the preparation in the step (1) is carried out, the phenol and the formaldehyde are dissolved in a sodium hydroxide solution, and the mixture is heated and stirred for 0.4-0.7 h at the temperature of 65-75 ℃.
Further, the mass ratio of the phenol used in the step (1), the P123 used in the step (2) and the F127 used in the step (2) is 1: 0.6-0.9: 1.1-1.5 in sequence;
further, in the step (2), during preparation, after mixing the template agents P123 and F127 and the oligomeric phenolic resin, stirring for 2-4 h at 65-75 ℃, cooling to room temperature, transferring the obtained solution into a hydrothermal kettle, carrying out hydrothermal reaction for 10-18 h at 100-130 ℃, cooling to room temperature, filtering and cleaning the obtained product, carrying out vacuum drying for 6-24 h at 50-80 ℃, roasting for 1.5-5 h at 550-800 ℃ under the protection of inert gas, cooling to room temperature, and grinding into powder to obtain the hierarchical porous carbon material; the inert gas is nitrogen or argon.
Further, the cobalt salt in the step (3) is Co (NO)3)2·6H2O、CoCl2·6H2O or Co (CH)3COO)2·4H2O；
Further, the nickel salt in the step (3) is Ni (NO)3)2·6H2O、NiCl2·6H2O or Ni (CH)3COO)2·4H2O；
Further, the manganese salt in the step (3) is Mn (NO)3)2·4H2O、MnCl2·4H2O or Mn (CH)3COO)2·4H2O。
Further, the precursor raw materials (cobalt salt, nickel salt, manganese salt, urea and NH) added in the step (3)4F) The solid-to-liquid ratio (mg/mL) of the ionic water to the ionic water is 10: 1-20: 1;
further, the solid-to-liquid ratio (mg/mL) of the nickel foam and the CoNiMn precursor liquid in the step (3) is 0.6: 1-0.9: 1.
Further, in the step (3), adding the cleaned nickel foam, fully soaking, performing hydrothermal treatment at 100-160 ℃ for 3-15 hours, cooling, filtering to obtain a product, cleaning with deionized water, and performing vacuum drying at 30-80 ℃ for 5-48 hours to obtain the CoNiMn precursor loaded on the nickel foam carrier.
Further, the cobalt salt, nickel salt, manganese salt, urea and NH in the steps (3) and (4)4F、Na2S·9H2The molar ratio of O is 2:1:1: 3-6: 3-10.
Further, in the step (4), Na2S·9H2The concentration of the O aqueous solution is 9-20 mg/mL;
further, the adding amount of the hierarchical porous carbon material in the step (4) is 10-50 mg of the hierarchical porous carbon material added to 1 mol of nickel salt;
further, the hierarchical porous carbon material of the step (4) is mixed with Na2S·9H2The solid-to-liquid ratio (mg/mL) of the O aqueous solution is 1: 1.6-1: 6;
further, in the step (4), the hierarchical porous carbon material prepared in the step (2) is added to Na2S·9H2And (3) performing ultrasonic treatment on the aqueous solution O for 2-10 hours, adding the CoNiMn precursor loaded on the nickel foam carrier prepared in the step (3), performing hydrothermal treatment on the mixture at the temperature of 130-190 ℃ for 5-15 hours, cooling to room temperature, filtering and washing the product, and performing vacuum drying at the temperature of 30-80 ℃ for 6-48 hours to obtain CoNiMn-S @ HPC.
The invention claims a high-performance supercapacitor electrode material prepared by the method.
The invention has the beneficial effects that:
1. the selected raw materials are cheap and easily available, expensive and toxic raw material reagents are avoided, and the method has the advantages of low process cost, no environmental pollution and the like.
2. The preparation method is a synthesis method which takes water as a solvent in a special sealed reaction container, and compared with other preparation methods, the hydrothermal method has the advantages of simple operation, mild conditions, easy control of reaction process, controllable material structure and performance, wide raw material selection range and the like. Moreover, the hydrothermal method adopted by the invention is simple and feasible, the process is controllable, no complex experimental equipment is needed, and the industrial large-scale production is easy to carry out.
3. The adopted nickel foam substrate not only can be used as a growth substrate of the hierarchical pore carbon coating CoNiMn-S nanowire, but also can be used as a current collector.
4. The adopted carbon material is a hierarchical porous carbon material with a micropore-mesopore-macropore structure, wherein the micropores can increase the specific surface area of the material, improve the utilization rate of the specific surface and increase the double electric layer capacitance of the material; the mesopores can provide a low-resistance channel for electrolyte ions to enter the electrode material; the large pores can store a large amount of electrolyte ions, and provide a short diffusion distance for the electrolyte to enter the inner surface of the material.
5. By adopting the hierarchical porous carbon to coat the CoNiMn-S nanowire, the structural stability of the CoNiMn-S in the electrochemical charge-discharge cycle process can be improved, the conductivity of the CoNiMn-S nanowire can be improved, rapid charge transmission is promoted, and the like, so that the electrochemical energy storage performance of the CoNiMn-S is effectively improved.
6. When the prepared hierarchical porous carbon coating CoNiMn-S nanowire material loaded on nickel foam is used as an electrode material of a super capacitor, the material shows high specific capacitance, good rate performance, low transmission resistance and excellent circulation stability, and has huge application potential in the field of super capacitors.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the CoNiMn-S @ HPC composite obtained in example 1.
FIG. 2 is a Transmission Electron Microscope (TEM) image of the CoNiMn-S @ HPC composite obtained in example 1.
FIG. 3 is a plot of Cyclic Voltammetry (CV) for the CoNiMn-S @ HPC composite electrode material obtained in example 1 at different sweep rates.
FIG. 4 shows the constant current charging and discharging (GCD) curves (a: 1A/g; b: 2A/g; c: 5A/g; d:10A/g) of the CoNiMn-S @ HPC composite electrode material obtained in example 1 at different current densities.
FIG. 5 is a graph of the cycling stability at a current density of 1A/g for the CoNiMn-S @ HPC composite electrode material obtained in example 1.
FIG. 6 is a Nyquist plot of the CoNiMn-S @ HPC composite electrode material obtained in example 1.
Detailed Description
The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.
Example 1: preparing a hierarchical porous carbon coating CoNiMn-S nanowire composite electrode material loaded on nickel foam
The method comprises the following steps:
(1) preparation of oligomeric phenolic resin Resol
Adding 1.0g of phenol and 2.5mL of 40% formaldehyde solution into 4mL of 0.5M NaOH solution, and stirring at 65 ℃ for 0.7h to obtain the oligomeric phenolic resin Resol.
(2) Preparation of hierarchical porous carbon materials (HPC)
0.6g P123 (EO)20PO70EO20)，1.1g F127(EO106PO70EO106) Adding the mixture into the oligomeric phenolic resin solution, stirring for 4h at 65 ℃, cooling to room temperature, transferring the obtained solution into a hydrothermal kettle, carrying out hydrothermal treatment for 18h at 100 ℃, filtering out the obtained material, repeatedly cleaning with distilled water, carrying out vacuum drying for 24h at 50 ℃, transferring into a tubular furnace, roasting for 1.5h at 800 ℃ under the protection of nitrogen gas, cooling to room temperature, and grinding to obtain the hierarchical porous carbon material.
(3) Preparation of CoNiMn precursor loaded on nickel foam carrier
290.9mg of Co (NO)3)2·6H2O,145.3mg Ni(NO3)2·6H2O,125.5mg Mn(NO3)2·4H2O,120mg Urea and 74mg NH4F, adding the mixture into 40ml of deionized water, stirring the mixture for 30 minutes, transferring the mixture into a hydrothermal kettle, and adding a piece of the mixtureCleaned nickel foam (size 0.9X 1.3X 0.1 cm)3And the mass is 34.2mg, the precursor is immersed for 1 hour and then hydrothermal for 6 hours at 130 ℃, the precursor is cooled to room temperature, a product is filtered, the product is washed by deionized water, and the product is dried in vacuum for 12 hours at 60 ℃, so that the CoNiMn precursor loaded on the nickel foam carrier is obtained.
(4) Preparation of hierarchical porous carbon coating CoNiMn-S nanowire loaded on nickel foam
480mg of Na2S·9H2Dissolving O in 40mL of deionized water, adding 20mg of the hierarchical porous carbon material prepared in the step (2), performing ultrasonic treatment for 4 hours, adding the CoNiMn precursor loaded on the nickel foam carrier prepared in the step (3), performing hydrothermal treatment on the mixture at 160 ℃ for 8 hours, cooling to room temperature, filtering and washing the product, and performing vacuum drying at 60 ℃ for 12 hours to obtain the hierarchical porous carbon coating CoNiMn-S nanowire material (CoNiMn-S @ HPC) loaded on the nickel foam.
Electrochemical performance test of CoNiMn-S @ HPC composite electrode material:
cyclic Voltammetry (CV), constant current charge and discharge (GCD) and Electrochemical Impedance (EIS) tests are performed on an electrochemical workstation by adopting a three-electrode system, wherein a hierarchical porous carbon coating CoNiMn-S nanowire loaded on nickel foam is directly used as a working electrode, a platinum sheet is used as a counter electrode, Hg/HgO is used as a reference electrode, and 3M KOH solution is used as electrolyte. The specific capacitance is calculated from the GCD curve.
Structural characterization and performance test of the CoNiMn-S @ HPC composite material:
FIG. 1 is a Scanning Electron Microscope (SEM) image of the resulting CoNiMn-S @ HPC composite. As can be seen from the figure, the resulting CoNiMn-S @ HPC nanowires were grown uniformly on a nickel foam substrate, and were approximately 2 μm in length, and the CoNiMn-S @ HPC nanowires were interconnected into a porous network structure with three-dimensional macropores, which provides not only convenient ion diffusion channels, but also promotes contact between ions and the active material.
The detailed morphology and microstructure of the resulting CoNiMn-S @ HPC composite was further characterized using Transmission Electron Microscopy (TEM), as shown in FIG. 2. According to TEM images, the CoNiMn-S @ HPC nanowires are about 60nm in diameter, rough in surface and obviously coated by a carbon layer, and the coated carbon layer can provide a high-speed charge and discharge charge transmission path, maintain the structural stability of the inorganic CoNiMn-S nanocrystals and prevent the volume change of the inorganic CoNiMn-S nanocrystals in the charge and discharge processes, so that the cycling stability of the CoNiMn-S electrode material is improved.
FIG. 3 is a Cyclic Voltammetry (CV) curve of the obtained CoNiMn-S @ HPC composite electrode material at different scanning speeds, and the scanning voltage is 0-0.6V. As can be seen from the figure, the CV curve of CoNiMn-S @ HPC has a distinct redox peak, and as the sweep rate is increased from 2mV/S to 10mV/S, the peak current also becomes larger, and the shapes of the redox peaks of the CV curves at different sweep rates are very similar.
FIG. 4 is a constant current charge and discharge (GCD) curve of the obtained CoNiMn-S @ HPC composite electrode material under different current densities. The specific capacitance of the CoNiMn-S @ HPC composite electrode material is 2103.1,1704.6,1175.4 and 876.5F/g respectively at current densities of 1,2,5 and 10A/g, and the CoNiMn-S @ HPC composite electrode material shows excellent specific capacitance and good rate performance.
FIG. 5 shows the cycling stability of the resulting CoNiMn-S @ HPC composite electrode material at a current density of 1A/g. After 2000 times of charge-discharge cycles, the specific capacitance retention rate of the CoNiMn-S @ HPC electrode material is 95.4%, which shows that the CoNiMn-S @ HPC electrode material has excellent cycle stability. Under the condition of the former 500 cycles, the specific capacitance is not reduced but slightly increased, which is mainly because the electrode is gradually activated after charging and discharging, the wettability of the electrode surface is improved, and the electrolyte ions are promoted to be diffused into micropores of the electrode, so that a larger electroactive specific surface area and a larger channel of the electrolyte ions are generated.
FIG. 6 is a Nyquist plot of the resulting CoNiMn-S @ HPC composite electrode material. The electrochemical impedance spectroscopy is used for researching the transmission resistance of the CoNiMn-S @ HPC composite electrode material, the Nyquist curve is shown in FIG. 6, and the inset is the Nyquist curve in the high-frequency region. The semi-circle has an intercept on the horizontal axis of equivalent series resistance (Rs) of 0.38 Ω, representing the sum of the resistance from the electrolyte and the interior of the active material, and the contact resistance between the active material and the current collector, which is relatively small, indicating that the supercapacitor has good rate capacity or power density. The diameter of the semicircle corresponds to the charge transfer resistance at the electrode-electrolyte interface, which is 0.15 Ω, indicating that the CoNiMn-S @ HPC composite electrode material has a lower charge transfer resistance and a higher conductivity. The Nyquist curve is in a shape close to a straight line in a low-frequency region, shows ideal capacitance behavior and lower ion diffusion resistance, and is mainly attributed to the hierarchical pore structure of HPC and the unique nanowire structure of CoNiMn-S @ HPC, so that the rapid diffusion of electrolyte ions is promoted, and the diffusion distance of the electrolyte ions in the charging and discharging processes is shortened.
Example 2: preparing a hierarchical porous carbon coating CoNiMn-S nanowire composite electrode material loaded on nickel foam
The method comprises the following steps:
(1) preparation of oligomeric phenolic resin Resol
1.0g of phenol and 4.5mL of 37% formaldehyde solution are added into 6mL of 0.5M NaOH solution, and the mixture is stirred for 0.4h at 75 ℃ to obtain the oligomeric phenolic resin Resol.
(2) Preparation of hierarchical porous carbon materials (HPC)
Adding 0.9g P123 and 1.5g F127 to the oligomeric phenolic resin, stirring for 2h at 75 ℃, cooling to room temperature, transferring the obtained solution to a hydrothermal kettle, carrying out hydrothermal reaction for 10h at 130 ℃, filtering the obtained material, repeatedly cleaning by using distilled water, carrying out vacuum drying for 6h at 80 ℃, transferring to a tubular furnace, roasting for 5h at 550 ℃ under the protection of nitrogen gas, cooling to room temperature, and grinding to obtain the hierarchical porous carbon material.
(3) Preparation of Ni-Co precursor loaded on nickel foam carrier
238.5mg CoCl2·6H2O,118.5mg NiCl2·6H2O,98.96mg MnCl2·4H2O,120mg Urea and 110mg NH4F, adding into 60ml deionized water, stirring for 30 minutes, transferring into a hydrothermal kettle, and adding a piece of cleaned nickel foam (the size is 1 multiplied by 1.5 multiplied by 0.1 cm)343.9mg, soaking for 1 hour, hydrothermal at 100 ℃ for 15 hours, cooling to room temperature, filtering to obtain a product, washing with deionized water, and vacuum drying at 30 ℃ for 48 hours to obtain the nickel-loaded foam carrierCoNiMn precursor on body.
(4) Preparation of hierarchical porous carbon coating CoNiMn-S nanowire loaded on nickel foam
960mg of Na2S·9H2Dissolving O in 60mL of deionized water, adding 10mg of the hierarchical porous carbon material prepared in the step (2), performing ultrasonic treatment for 2 hours, adding the CoNiMn precursor loaded on the nickel foam carrier prepared in the step (3), performing hydrothermal treatment on the mixture at 130 ℃ for 15 hours, cooling to room temperature, filtering and washing the product, and performing vacuum drying at 50 ℃ for 20 hours to obtain the hierarchical porous carbon coating CoNiMn-S nanowire material (CoNiMn-S @ HPC) loaded on the nickel foam.
Electrochemical performance test of CoNiMn-S @ HPC composite electrode material:
cyclic Voltammetry (CV), constant current charge and discharge (GCD) and Electrochemical Impedance (EIS) tests are performed on an electrochemical workstation by adopting a three-electrode system, wherein a hierarchical porous carbon coating CoNiMn-S nanowire loaded on nickel foam is directly used as a working electrode, a platinum sheet is used as a counter electrode, Hg/HgO is used as a reference electrode, and 3M KOH solution is used as electrolyte. The specific capacitance is calculated from the GCD curve.
Structural characterization and performance test of the CoNiMn-S @ HPC composite material:
the resulting CoNiMn-S @ HPC nanowires were grown uniformly on a nickel foam substrate to a length of about 2.1 μm, and were interconnected into a porous network structure with three-dimensional macropores, which provided not only convenient ion diffusion channels, but also facilitated contact between the ions and the active material.
The CoNiMn-S @ HPC nanowire has the diameter of about 62nm, is rough in surface and is obviously coated by a carbon layer, and the coated carbon layer can provide a high-speed charge and discharge charge transmission path, maintain the structural stability of the inorganic CoNiMn-S nanocrystal and prevent the volume change of the inorganic CoNiMn-S nanocrystal in the charge and discharge processes, so that the cycle stability of the CoNiMn-S electrode material is improved.
The CV curve of CoNiMn-S @ HPC has a distinct redox peak, and as the sweep rate is increased from 2mV/S to 10mV/S, the peak current also increases, and the shapes of the redox peaks of the CV curves at different sweep rates are very similar. The specific capacitance of the CoNiMn-S @ HPC composite electrode material is 1742.4,1458.7,1154.5 and 849.8F/g respectively at current densities of 1,2,5 and 10A/g, and the CoNiMn-S @ HPC composite electrode material shows excellent specific capacitance and good rate performance.
After 2000 times of charge-discharge cycles, the specific capacitance retention rate of the CoNiMn-S @ HPC electrode material is 93.9%, which shows that the CoNiMn-S @ HPC electrode material has excellent cycle stability. Under the condition of the previous 500 cycles, the specific capacitance is not reduced but slightly increased, which is mainly because the electrode is gradually activated after being charged and discharged, so that the wettability of the surface of the electrode is improved, and electrolyte ions are promoted to be diffused into micropores of the electrode, thereby generating larger specific surface area of electric activity and larger channels of the electrolyte ions.
The transmission resistance condition of the CoNiMn-S @ HPC composite electrode material is researched by adopting an electrochemical impedance spectrum, the intercept of a Nyquist curve semicircle on the horizontal axis is 0.45 omega, and the resistance from the inside of an electrolyte and an active material and the contact resistance between the active material and a current collector are relatively small. The semi-circle diameter was 0.19 Ω, indicating that the CoNiMn-S @ HPC composite electrode material had a lower charge transport resistance and a higher conductivity. The Nyquist curve is in a shape close to a straight line in a low-frequency region, shows ideal capacitance behavior and lower ion diffusion resistance, and is mainly attributed to the hierarchical pore structure of HPC and the unique nanowire structure of CoNiMn-S @ HPC, so that the rapid diffusion of electrolyte ions is promoted, and the diffusion distance of the electrolyte ions in the charging and discharging processes is shortened.
Example 3: preparing a hierarchical porous carbon coating CoNiMn-S nanowire composite electrode material loaded on nickel foam
The method comprises the following steps:
(1) preparation of oligomeric phenolic resin Resol
Adding 1.0g of phenol and 3.5mL of 39% formaldehyde solution into 5mL of 0.5M NaOH solution, and stirring at 65 ℃ for 0.7h to obtain the oligomeric phenolic resin Resol.
(2) Preparation of a hierarchical porous Material (HPC)
Adding 0.85g P123 and 1.15g F127 into the oligomeric phenolic resin, stirring for 3h at 70 ℃, cooling to room temperature, transferring the obtained solution into a hydrothermal kettle, carrying out hydrothermal treatment for 15h at 120 ℃, filtering the obtained material, repeatedly cleaning by using distilled water, carrying out vacuum drying for 15h at 60 ℃, transferring into a tubular furnace, roasting for 4h at 700 ℃ under the protection of argon gas, cooling to room temperature, and grinding to obtain the hierarchical porous carbon material.
(3) Preparation of a CoNiMn precursor supported on a nickel foam support: 248.9mg of Co (CH)3COO)2·4H2O,125.6mg Ni(CH3COO)2·4H2O,122.5mg Mn(CH3COO)2·4H2O,100mg Urea and 60mg NH4F, adding the mixture into 40ml of deionized water, stirring the mixture for 30 minutes, transferring the mixture into a hydrothermal kettle, and adding a piece of cleaned nickel foam (the size is 1 multiplied by 1.5 multiplied by 0.1 cm)3And the mass is 43.9mg, the precursor is immersed for 1 hour and then is hydrothermal at 150 ℃ for 5 hours, the mixture is cooled to room temperature, a product is filtered, deionized water is adopted for cleaning, and vacuum drying is carried out at 80 ℃ for 6 hours, so that the CoNiMn precursor loaded on the nickel foam carrier is obtained.
(4) Preparation of hierarchical porous carbon coating CoNiMn-S nanowires loaded on nickel foam: adding 360mg of Na2S·9H2Dissolving O in 40mL of deionized water, adding 25mg of the hierarchical porous carbon material prepared in the step (2), performing ultrasonic treatment for 2 hours, adding the CoNiMn precursor loaded on the nickel foam carrier prepared in the step (3), performing hydrothermal treatment on the mixture at 150 ℃ for 10 hours, cooling to room temperature, filtering and washing the product, and performing vacuum drying at 80 ℃ for 6 hours to obtain the hierarchical porous carbon coating CoNiMn-S nanowire material (CoNiMn-S @ HPC) loaded on the nickel foam.
Electrochemical performance test of CoNiMn-S @ HPC composite electrode material:
cyclic Voltammetry (CV), constant current charge and discharge (GCD) and Electrochemical Impedance (EIS) tests are performed on an electrochemical workstation by adopting a three-electrode system, wherein a hierarchical porous carbon coating CoNiMn-S nanowire loaded on nickel foam is directly used as a working electrode, a platinum sheet is used as a counter electrode, Hg/HgO is used as a reference electrode, and 3M KOH solution is used as electrolyte. The specific capacitance is calculated from the GCD curve.
Structural characterization and performance test of the CoNiMn-S @ HPC composite material:
the resulting CoNiMn-S @ HPC nanowires were grown uniformly on a nickel foam substrate to a length of about 2.2 μm, and were interconnected into a porous network with three-dimensional macropores, a special interconnected network that not only provided convenient ion diffusion channels, but also facilitated contact between the ions and the active material.
The CoNiMn-S @ HPC nanowire has the diameter of about 70nm, is rough in surface and is obviously coated by a carbon layer, and the coated carbon layer can provide a high-speed charge and discharge charge transmission path, maintain the structural stability of the inorganic CoNiMn-S nanocrystal and prevent the volume change of the inorganic CoNiMn-S nanocrystal in the charge and discharge processes, so that the cycle stability of the CoNiMn-S electrode material is improved.
The CV curve of CoNiMn-S @ HPC has a distinct redox peak, and as the sweep rate is increased from 2mV/S to 10mV/S, the peak current also increases, and the shapes of the redox peaks of the CV curves at different sweep rates are very similar. The specific capacitance of the CoNiMn-S @ HPC composite electrode material is 1611.1, 1338.2, 1006.3 and 783.7F/g at current densities of 1,2,5 and 10A/g respectively, and the CoNiMn-S @ HPC composite electrode material shows excellent specific capacitance and good rate performance.
After 2000 times of charge-discharge cycles, the specific capacitance retention rate of the CoNiMn-S @ HPC electrode material is 92.8%, which shows that the CoNiMn-S @ HPC electrode material has excellent cycle stability. Under the condition of the previous 500 cycles, the specific capacitance is not reduced but slightly increased, which is mainly because the electrode is gradually activated after being charged and discharged, so that the wettability of the surface of the electrode is improved, and electrolyte ions are promoted to be diffused into micropores of the electrode, thereby generating larger specific surface area of electric activity and larger channels of the electrolyte ions.
The transmission resistance condition of the CoNiMn-S @ HPC composite electrode material is researched by adopting an electrochemical impedance spectrum, the intercept of a Nyquist curve semicircle on the horizontal axis is 0.47 omega, and the resistance from the inside of an electrolyte and an active material and the contact resistance between the active material and a current collector are relatively small. The diameter of the semicircle is 0.2 omega, which shows that the CoNiMn-S @ HPC composite electrode material has lower charge transfer resistance and higher conductivity. The Nyquist curve is in a shape close to a straight line in a low-frequency region, shows ideal capacitance behavior and lower ion diffusion resistance, and is mainly attributed to the hierarchical pore structure of HPC and the unique nanowire structure of CoNiMn-S @ HPC, so that the rapid diffusion of electrolyte ions is promoted, and the diffusion distance of the electrolyte ions in the charging and discharging processes is shortened.
Example 4: preparing a hierarchical porous carbon coating CoNiMn-S nanowire composite electrode material loaded on nickel foam
The method comprises the following steps:
(1) preparation of oligomeric phenolic resin Resol
Adding 1.0g of phenol and 4.0mL of formaldehyde solution with the concentration of 37% into 5mL0.5M NaOH solution, and stirring at 70 ℃ for 0.6h to obtain the oligomeric phenolic resin Resol.
(2) Preparation of hierarchical porous carbon materials (HPC)
Adding 0.75g P123 and 1.25g F127 into the oligomeric phenolic resin, stirring for 3h at 70 ℃, cooling to room temperature, transferring the obtained solution into a hydrothermal kettle, carrying out hydrothermal treatment for 18h at 100 ℃, filtering the obtained material, repeatedly cleaning by using distilled water, carrying out vacuum drying for 20h at 50 ℃, transferring into a tubular furnace, roasting for 3h at 700 ℃ under the protection of nitrogen gas, cooling to room temperature, and grinding to obtain the hierarchical porous carbon material.
(3) Preparation of CoNiMn precursor loaded on nickel foam carrier
291.2mg of Co (NO)3)2·6H2O,145.5mg Ni(NO3)2·6H2O,125.1mg Mn(NO3)2·4H2O,180mg Urea and 110mg NH4F, adding into 60ml deionized water, stirring for 30 minutes, transferring into a hydrothermal kettle, and adding a piece of cleaned nickel foam (with the size of 0.9 multiplied by 1.3 multiplied by 0.1 cm)3And the mass is 34.2mg, the precursor is immersed for 1 hour and then is hydrothermal at 130 ℃ for 10 hours, the mixture is cooled to room temperature, a product is filtered, deionized water is adopted for cleaning, and vacuum drying is carried out at 70 ℃ for 10 hours, so that the CoNiMn precursor loaded on the nickel foam carrier is obtained.
(4) Preparation of hierarchical porous carbon coating CoNiMn-S nanowire loaded on nickel foam
1200mg of Na2S·9H2Dissolving O in 60mL of deionized water, adding 25mg of the hierarchical porous carbon material prepared in the step (2), performing ultrasonic treatment for 4 hours, adding the CoNiMn precursor loaded on the nickel foam carrier prepared in the step (3), performing hydrothermal treatment on the mixture at 140 ℃ for 12 hours, cooling to room temperature, filtering and washing the product, and performing vacuum drying at 60 ℃ for 15 hours to obtain the hierarchical porous carbon coating CoNiMn-S nanowire material (CoNiMn-S @ HPC) loaded on the nickel foam.
Electrochemical performance test of CoNiMn-S @ HPC composite electrode material:
cyclic Voltammetry (CV), constant current charge and discharge (GCD) and Electrochemical Impedance (EIS) tests are performed on an electrochemical workstation by adopting a three-electrode system, wherein a hierarchical porous carbon coating CoNiMn-S nanowire loaded on nickel foam is directly used as a working electrode, a platinum sheet is used as a counter electrode, Hg/HgO is used as a reference electrode, and 3M KOH solution is used as electrolyte. The specific capacitance is calculated from the GCD curve.
Structural characterization, performance testing and discussion of CoNiMn-S @ HPC composites:
the resulting CoNiMn-S @ HPC nanowires were grown uniformly on a nickel foam substrate to a length of about 2.2 μm, and were interconnected into a porous network with three-dimensional macropores, a special interconnected network that not only provided convenient ion diffusion channels, but also facilitated contact between the ions and the active material.
The CoNiMn-S @ HPC nanowire has the diameter of about 65nm, is rough in surface and is obviously coated by a carbon layer, and the coated carbon layer can provide a high-speed charge and discharge charge transmission path, maintain the structural stability of the inorganic CoNiMn-S nanocrystal and prevent the volume change of the inorganic CoNiMn-S nanocrystal in the charge and discharge processes, so that the cycle stability of the CoNiMn-S electrode material is improved.
The CV curve of CoNiMn-S @ HPC has a distinct redox peak, and as the sweep rate is increased from 2mV/S to 10mV/S, the peak current also increases, and the shapes of the redox peaks of the CV curves at different sweep rates are very similar. The specific capacitance of the CoNiMn-S @ HPC composite electrode material is 1903.8, 1530.5, 1030.7 and 823.5F/g respectively at current densities of 1,2,5 and 10A/g, and the CoNiMn-S @ HPC composite electrode material shows excellent specific capacitance and good rate performance.
After 2000 times of charge-discharge cycles, the specific capacitance retention rate of the CoNiMn-S @ HPC electrode material is 94.2%, which shows that the CoNiMn-S @ HPC electrode material has excellent cycle stability. Under the condition of the previous 500 cycles, the specific capacitance is not reduced but slightly increased, which is mainly because the electrode is gradually activated after being charged and discharged, so that the wettability of the surface of the electrode is improved, and electrolyte ions are promoted to be diffused into micropores of the electrode, thereby generating larger specific surface area of electric activity and larger channels of the electrolyte ions.
The transmission resistance condition of the CoNiMn-S @ HPC composite electrode material is researched by adopting an electrochemical impedance spectrum, the intercept of a Nyquist curve semicircle on the horizontal axis is 0.4 omega, and the resistance from the inside of an electrolyte and an active material and the contact resistance between the active material and a current collector are relatively small. The semi-circle diameter was 0.17 Ω, indicating that the CoNiMn-S @ HPC composite electrode material has a lower charge transport resistance and a higher conductivity. The Nyquist curve is in a shape close to a straight line in a low-frequency region, shows ideal capacitance behavior and lower ion diffusion resistance, and is mainly attributed to the hierarchical pore structure of HPC and the unique nanowire structure of CoNiMn-S @ HPC, so that the rapid diffusion of electrolyte ions is promoted, and the diffusion distance of the electrolyte ions in the charging and discharging processes is shortened.
Example 5: preparing a hierarchical porous carbon coating CoNiMn-S nanowire composite electrode material loaded on nickel foam
The method comprises the following steps:
(1) preparation of oligomeric phenolic resin Resol
Adding 1.0g of phenol and 3.5mL of 40% formaldehyde solution into 5mL of 0.5M NaOH solution, and stirring at 70 ℃ for 0.5h to obtain the oligomeric phenolic resin Resol.
(2) Preparation of hierarchical porous carbon materials (HPC)
Adding 0.75g P123 and 1.25g F127 into the oligomeric phenolic resin, stirring for 3h at 70 ℃, cooling to room temperature, transferring the obtained solution into a hydrothermal kettle, carrying out hydrothermal treatment for 18h at 100 ℃, filtering the obtained material, repeatedly cleaning by using distilled water, carrying out vacuum drying for 15h at 60 ℃, transferring into a tubular furnace, roasting for 3h at 700 ℃ under the protection of argon gas, cooling to room temperature, and grinding to obtain the hierarchical porous carbon material.
(3) Preparation of CoNiMn precursor Supported on Nickel foam support
290.5mg of Co (NO)3)2·6H2O,145.5mg Ni(NO3)2·6H2O,125.8mg Mn(NO3)2·4H2O,150mg Urea and 90mg NH4F, adding the mixture into 65ml of deionized water, stirring the mixture for 30 minutes, transferring the mixture into a hydrothermal kettle, and adding a piece of cleaned nickel foam (the size is 1.05 multiplied by 1.4 multiplied by 0.1 cm)3The mass of the precursor is 42.9mg, the precursor is immersed for 1 hour and then is hydrothermally treated for 13 hours at 110 ℃, the mixture is cooled to room temperature, a product is filtered, the product is washed by deionized water, and the product is dried in vacuum at 40 ℃ for 36 hours, so that the CoNiMn precursor loaded on the nickel foam carrier is obtained.
(4) Preparation of hierarchical porous carbon coating CoNiMn-S nanowire loaded on nickel foam
720mg of Na2S·9H2Dissolving O in 65mL of deionized water, adding 15mg of the hierarchical porous carbon material prepared in the step (2), performing ultrasonic treatment for 6 hours, adding the CoNiMn precursor loaded on the nickel foam carrier prepared in the step (3), performing hydrothermal treatment on the mixture at 130 ℃ for 15 hours, cooling to room temperature, filtering and washing the product, and performing vacuum drying at 40 ℃ for 36 hours to obtain the hierarchical porous carbon coating CoNiMn-S nanowire material (CoNiMn-S @ HPC) loaded on the nickel foam.
Electrochemical performance test of CoNiMn-S @ HPC composite electrode material:
cyclic Voltammetry (CV), constant current charge and discharge (GCD) and Electrochemical Impedance (EIS) tests are performed on an electrochemical workstation by adopting a three-electrode system, wherein a hierarchical porous carbon coating CoNiMn-S nanowire loaded on nickel foam is directly used as a working electrode, a platinum sheet is used as a counter electrode, Hg/HgO is used as a reference electrode, and 3M KOH solution is used as electrolyte. The specific capacitance is calculated from the GCD curve.
Structural characterization and performance test of the CoNiMn-S @ HPC composite material:
the resulting CoNiMn-S @ HPC nanowires were grown uniformly on a nickel foam substrate to a length of about 2.2 μm, and were interconnected into a porous network with three-dimensional macropores, a special interconnected network that not only provided convenient ion diffusion channels, but also facilitated contact between the ions and the active material.
The CoNiMn-S @ HPC nanowire has the diameter of about 75nm, is rough in surface and is obviously coated by a carbon layer, and the coated carbon layer can provide a high-speed charge and discharge charge transmission path, maintain the structural stability of the inorganic CoNiMn-S nanocrystal and prevent the volume change of the inorganic CoNiMn-S nanocrystal in the charge and discharge processes, so that the cycle stability of the CoNiMn-S electrode material is improved.
The CV curve of CoNiMn-S @ HPC has a distinct redox peak, and as the sweep rate is increased from 2mV/S to 10mV/S, the peak current also increases, and the shapes of the redox peaks of the CV curves at different sweep rates are very similar. The specific capacitance of the CoNiMn-S @ HPC composite electrode material is 1840.9,1485.2, 1010.9 and 779.7F/g respectively at current densities of 1,2,5 and 10A/g, and the CoNiMn-S @ HPC composite electrode material shows excellent specific capacitance and good rate performance.
After 2000 times of charge-discharge cycles, the specific capacitance retention rate of the CoNiMn-S @ HPC electrode material is 94%, which shows that the CoNiMn-S @ HPC electrode material has excellent cycle stability. Under the condition of the previous 500 cycles, the specific capacitance is not reduced but slightly increased, which is mainly because the electrode is gradually activated after being charged and discharged, so that the wettability of the surface of the electrode is improved, and electrolyte ions are promoted to be diffused into micropores of the electrode, thereby generating larger specific surface area of electric activity and larger channels of the electrolyte ions.
The electrochemical impedance spectroscopy is adopted to study the transmission resistance of the CoNiMn-S @ HPC composite electrode material, the intercept of the semi-circle of the Nyquist curve on the horizontal axis is 0.42 omega, and the resistance from the electrolyte and the interior of the active material and the contact resistance between the active material and the current collector are relatively small. The semi-circle diameter was 0.18 Ω, indicating that the CoNiMn-S @ HPC composite electrode material had a lower charge transport resistance and a higher conductivity. The Nyquist curve is in a shape close to a straight line in a low-frequency region, shows ideal capacitance behavior and lower ion diffusion resistance, and is mainly attributed to the hierarchical pore structure of HPC and the unique nanowire structure of CoNiMn-S @ HPC, so that the rapid diffusion of electrolyte ions is promoted, and the diffusion distance of the electrolyte ions in the charging and discharging processes is shortened.
Claims (10)
1. A preparation method of a high-performance super capacitor electrode material is characterized by comprising the following steps: the method comprises the following steps:
(1) the preparation of the oligomeric phenolic resin comprises the following steps: dissolving phenol and formaldehyde in a sodium hydroxide solution, heating and stirring to prepare oligomeric phenolic resin;
(2) preparing a hierarchical porous carbon material: adding template agents P123 and F127 into the oligomeric phenolic resin prepared in the step (1), stirring to react, cooling to room temperature, transferring the obtained product into a hydrothermal kettle, separating a solid product after the hydrothermal reaction is finished and the cooling to room temperature, roasting the solid product under the protection of inert gas, cooling, and grinding into powder to obtain the hierarchical porous carbon material;
(3) preparing a precursor: cobalt salt, nickel salt, manganese salt, urea and NH4F is added into deionized water to prepare a CoNiMn precursor;
transferring the CoNiMn precursor into a hydrothermal kettle, adding nickel foam, fully reacting, and cleaning a filtered product to obtain the CoNiMn precursor loaded on a nickel foam carrier;
(4) preparing a hierarchical porous carbon coating CoNiMn-S nanowire loaded on nickel foam: adding the hierarchical porous carbon material prepared in the step (2) into Na2S·9H2And (3) adding the CoNiMn precursor loaded on the nickel foam carrier prepared in the step (3) into the O aqueous solution, cooling to room temperature after the mixture is subjected to hydrothermal reaction, and filtering, washing and drying the product to obtain the hierarchical porous carbon coating cobalt nickel manganese sulfide nanowire composite electrode material (CoNiMn-S @ HPC) loaded on the nickel foam.
2. The preparation method of the high-performance supercapacitor electrode material according to claim 1, characterized in that: the using amount of the sodium hydroxide solution in the step (1) is 4-6 ml of 0.5M sodium hydroxide solution per 1g of phenol;
the dosage of the formaldehyde solution is 2.5-4.5 ml of formaldehyde solution with the concentration of 37-40% for every 1g of phenol;
during preparation, the phenol and the formaldehyde are dissolved in a sodium hydroxide solution, and the mixture is heated and stirred for 0.4-0.7 h at the temperature of 65-75 ℃.
3. The preparation method of the high-performance supercapacitor electrode material according to claim 1 or 2, characterized by comprising the following steps:
the mass ratio of the phenol used in the step (1), the P123 used in the step (2) and the F127 used in the step (2) is 1: 0.6-0.9: 1.1-1.5 in sequence.
4. The preparation method of the high-performance supercapacitor electrode material according to claim 1, characterized in that: in the preparation step (2), after mixing the template agents P123 and F127 and the oligomeric phenolic resin, stirring for 2-4 h at 65-75 ℃, cooling to room temperature, transferring the obtained solution into a hydrothermal kettle, carrying out hydrothermal reaction for 10-18 h at 100-130 ℃, cooling to room temperature, filtering and cleaning the obtained product, carrying out vacuum drying for 6-24 h at 50-80 ℃, roasting for 1.5-5 h at 550-800 ℃ under the protection of inert gas, cooling to room temperature, and grinding into powder to obtain the hierarchical porous carbon material; the inert gas is nitrogen or argon.
5. The preparation method of the high-performance supercapacitor electrode material according to claim 1 or 3, wherein the preparation method comprises the following steps:
the cobalt salt in the step (3) is Co (NO)3)2·6H2O、CoCl2·6H2O or Co (CH)3COO)2·4H2O；
The nickel salt in the step (3) is Ni (NO)3)2·6H2O、NiCl2·6H2O or Ni (CH)3COO)2·4H2O；
The manganese salt in the step (3) is Mn (NO)3)2·4H2O、MnCl2·4H2O or Mn (CH)3COO)2·4H2O。
The solid-liquid ratio of the precursor raw material to the ionized water in the step (3) is 10: 1-20: 1;
and (4) the solid-to-liquid ratio of the nickel foam to the CoNiMn precursor liquid in the step (3) is 0.6: 1-0.9: 1.
6. The preparation method of the high-performance supercapacitor electrode material according to claim 1, characterized in that: and (3) adding the cleaned nickel foam, fully soaking, performing hydrothermal treatment at 100-160 ℃ for 3-15 hours, cooling, filtering out a product, cleaning with deionized water, and performing vacuum drying at 30-80 ℃ for 5-48 hours to obtain a CoNiMn precursor loaded on the nickel foam carrier.
7. The preparation method of the high-performance supercapacitor electrode material according to claim 1, characterized in that: cobalt salt, nickel salt, manganese salt, urea and NH in the steps (3) and (4)4F、Na2S·9H2The molar ratio of O is 2:1:1: 3-6: 3-10.
8. The preparation method of the high-performance supercapacitor electrode material according to claim 1, characterized in that:
in step (4), Na2S·9H2The concentration of the O water solution is 9-20 mg/mL;
the adding amount of the hierarchical porous carbon material in the step (4) is 10-50 mg of the hierarchical porous carbon material added to every 1 mol of nickel salt;
the hierarchical porous carbon material obtained in the step (4) and Na2S·9H2The solid-liquid ratio of the O aqueous solution is 1: 1.6-1: 6.
9. The preparation method of the high-performance supercapacitor electrode material according to claim 1, characterized in that: in the step (4), the hierarchical porous carbon material prepared in the step (2) is added to Na2S·9H2Performing ultrasonic treatment for 2-10 hours in the presence of O aqueous solution, adding the CoNiMn precursor loaded on the nickel foam carrier prepared in the step (3), performing hydrothermal treatment on the mixture at the temperature of 130-190 ℃ for 5-15 hours, and coolingAnd cooling to room temperature, filtering and washing the product, and drying in vacuum at 30-80 ℃ for 6-48 hours to obtain the CoNiMn-S @ HPC.
10. A high-performance supercapacitor electrode material prepared by the method according to any one of claims 1 to 9.
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| CAO, JH; HU, YZ; CHEN, HC: ""Synthesis of mesoporous nickel-cobalt-manganese sulfides as electroactive materials for hybrid supercapacitors"", 《CHEMICAL ENGINEERING JOURNAL》, vol. 405, pages 1 - 2 * |
| LIU, YR; NIU, SY AND HU, R: ""Construction of hierarchical porous carbon coated NiCo2S4 nanowire composites for high-performance supercapacitors"", JOURNAL OF POROUS MATERIALS, vol. 28, no. 5, pages 1345 - 1352 * |
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