CN114783786B - Bimetal selenide-porous carbon composite material for super capacitor and preparation method and application thereof - Google Patents
Bimetal selenide-porous carbon composite material for super capacitor and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 239000003990 capacitor Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract description 17
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 8
- PYHYDDIOBZRCJU-UHFFFAOYSA-N [Ni]=[Se].[Co] Chemical compound [Ni]=[Se].[Co] PYHYDDIOBZRCJU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 5
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 claims abstract description 4
- AHBDJJPEQJQYMC-UHFFFAOYSA-N ethanol nickel(2+) dinitrate Chemical compound C(C)O.[N+](=O)([O-])[O-].[Ni+2].[N+](=O)([O-])[O-] AHBDJJPEQJQYMC-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 29
- 244000241796 Christia obcordata Species 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 8
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229960001471 sodium selenite Drugs 0.000 claims description 7
- 235000015921 sodium selenite Nutrition 0.000 claims description 7
- 239000011781 sodium selenite Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000005539 carbonized material Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 238000002484 cyclic voltammetry Methods 0.000 description 13
- 239000002135 nanosheet Substances 0.000 description 13
- 238000001000 micrograph Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 7
- 150000004771 selenides Chemical class 0.000 description 7
- -1 transition metal chalcogenides Chemical class 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
Abstract
A bimetal selenide-porous carbon composite material for a super capacitor, a preparation method and application thereof, wherein an activated three-dimensional porous carbon skeleton is used as a base material, cobalt nitrate and 2-methylimidazole are reacted on the surface of the carbon skeleton, and Co-MOF uniformly grows on the porous carbon skeleton; immersing the mixture into nickel nitrate ethanol solution to prepare cobalt nickel hydroxide which grows on a carbon skeleton; and then the porous carbon loaded cobalt-nickel selenide composite material is prepared through hydrothermal selenization. The composite material can effectively prevent active substances from stacking and falling off, improves the stability of redox active sites and structures, shows excellent multiplying power and cycle performance as an electrode material of a supercapacitor, has the advantages of green solvent, simple process, short reaction, high yield and the like, and has good application prospect.
Description
Technical Field
The invention relates to a bimetal selenide-porous carbon composite material for a super capacitor, and a preparation method and application thereof, and belongs to the technical field of new materials.
Background
To achieve the goals of carbon peaking and carbon neutralization, efforts have been directed toward developing clean and renewable energy conversion and storage systems, such as Super Capacitors (SCs), lithium Ion Batteries (LIBs), and the like. Lithium ion batteries and supercapacitors in energy storage devices have become research hotspots by virtue of their own advantages. As a novel energy storage device, the super capacitor has the advantages of high power density, high charging speed, long cycle life, environmental friendliness, safety and the like. Based on the energy storage mechanism of the super capacitor, the electrode material plays a decisive role in improving the performance of the super capacitor.
In recent years, transition metal chalcogenides have become viable alternatives to graphite bifunctional electrode materials in supercapacitors due to their large theoretical specific capacity and multiple valence statesEnergy Stor. Mater. 2020, 31, 252.]. The transition metal selenides have higher ion diffusion kinetics (1×10) -5 S∙m -1 ) And higher electrode conductivity (1×10) -3 S∙m -1 ) This facilitates stable and reliable operation in supercapacitorsNano Res. 2021, 14, 896-896.]. For example, snSe nanoplatelets prepared by liquid phase technique are 0.5. 0.5A ∙ g -1 When having 228 g F ∙ g -1 High specific capacitance of 10A ∙ g -1 When having 117F ∙ g -1 Is 1.0A ∙ g -1 99.0% initial Capacity Retention after the next 1000 cycles [ACS Nano, 2014, 8, 3761-3770.]. Cobalt zinc selenide (ZCS) as a battery type super capacitor electrode material, 2 g A ∙ g -1 When having 1419C ∙ g -1 And ZCS// AC battery-supercapacitor hybrid device achieved a wide potential window of 1.6V and 77.78 Wh kg -1 Is of 222W ∙ kg -1 The initial capacity retention after 10000 cycles is still as high as 80% [J. Energy Storage, 2020, 31: 101663.]. However, the transition metal selenide electrode materials face problems of low conductivity, slow ion/electron transport kinetics, and low cycling stability, impeding their practical use [ the following ]Chem. Eng. J., 2019, 364, 320.]。
For the above-mentioned problems to be solved urgently, reasonable structural design and composite engineering are viable strategies. If the electrode active material is designed into a two-dimensional ultrathin structure, the volume expansion can be relieved, the electron transmission rate is facilitated, and the number of active sites is increased; meanwhile, the transition metal selenide and the three-dimensional porous carbon skeleton can be strongly compounded to adapt to volume expansion. The three-dimensional porous Ni-Co-Se/C composite material is used as the electrode material of the super capacitor to show excellent multiplying power and cycle performance by utilizing the unique hierarchical structure and the synergistic effect of the bimetallic selenide.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a bimetal selenide-porous carbon composite material for a super capacitor, a preparation method and application thereof, and the prepared three-dimensional porous Ni-Co-Se/C composite material is beneficial to exposing redox active sites, and an ordered pore array ensures sufficient contact between an electrode and electrolyte. In addition, the unique structure makes the ion/electron transfer and diffusion between the three-dimensional porous carbon skeleton and Ni-Co-Se more effective, and the electrochemical reaction kinetics are effectively accelerated. The Ni-Co-Se/C composite material is applied to a super capacitor and has excellent multiplying power and cycle stability.
In order to solve the problems in the prior art, the invention adopts the following technical scheme:
a bimetal selenide-porous carbon composite material for a super capacitor comprises the following specific steps:
step 1, respectively preparing a 2-methylimidazole solution and a cobalt nitrate solution, pouring the cobalt nitrate solution into the 2-methylimidazole solution under a stirring state to obtain a mixed solution, placing the mixed solution into a microwave oven for treatment, immersing a three-dimensional porous carbon skeleton which is used as a substrate and subjected to hydrophilic treatment into the mixed solution for reaction for 25 minutes, taking out, washing and drying to obtain Co-MOF which uniformly grows on the porous carbon skeleton and is marked as Co-MOF/C;
step 2, immersing Co-MOF/C into an ethanol solution of nickel nitrate to obtain cobalt nickel hydroxide which grows on a three-dimensional porous carbon skeleton and is marked as Ni-Co-OH/C;
and 3, preparing a sodium nitrite solution, adding hydrazine hydrate 1.1 mmol/L to enable the concentration of the solution, immersing the Ni-Co-OH/C prepared in the step 2 into the solution, transferring the solution into a hydrothermal reaction kettle to react at 140-180 ℃, naturally cooling the reaction kettle, taking out the product, washing and drying the product, and obtaining the porous carbon loaded cobalt-nickel selenide composite material, which is marked as Ni-Co-Se/C.
As an improvement, the three-dimensional porous carbon skeleton is derived from butterfly wing derived carbonized materials.
As an improvement, the concentration of the cobalt nitrate is 0.04-0.06 mol/L, the concentration of the 2-methylimidazole is 0.4 mol/L, the concentration of the nickel nitrate is 1 mmol/L, and the concentration of the sodium selenite is 8-9 mmol/L.
The bimetal selenide-porous carbon composite material prepared based on the method.
The application of the bimetal selenide-porous carbon composite material in preparing the super capacitor.
The beneficial effects are that:
compared with the prior art, the bimetal selenide-porous carbon composite material for the super capacitor and the preparation method and application thereof have the following advantages:
(1) The cobalt nickel selenide nano-sheet growing on the butterfly wing-derived three-dimensional porous carbon skeleton is prepared by the microwave precipitation, ion exchange and hydrothermal selenization technology. In the preparation process, the ligand of Co-MOF can be removed uniformly, and the metal center is left to combine with hydroxide ions in the solution, so as to obtain Co-Ni-OH intermediate; and then selenizing, wherein most of the product inherits the structural characteristics of Co-Ni-OH nano-sheets, and part of the ultra-thin nano-sheets are obtained through hydroxide dissolution and selenization. The three-dimensional porous structure of the carbon can effectively ensure the full contact between the electrolyte and the electrode material; since MOFs grown on carbon backbones provide uniform and limited "metal seeds," forming two-dimensional nanoplatelet structures, volume expansion can be mitigated, facilitating electron transport rates, and increasing the number of active sites; the Ni-Co-Se nano sheet is uniformly and firmly anchored on the three-dimensional carbon skeleton, and can prevent the agglomeration and the falling of the active material, thereby effectively improving the structural stability. The unique multi-stage structure and the synergistic effect of the bimetallic selenide enable the material to show excellent cycle stability and rate capability when being applied to super capacitors;
(2) The carbon source adopted by the invention is butterfly wing derived carbon, has a natural three-dimensional ordered porous structure, has the advantages of environmental friendliness, wide sources, low cost, easy obtainment and the like, and combines the room-temperature deposition self-assembly, ion exchange and hydrothermal selenization technology to prepare the cobalt nickel selenide nano-sheets on the three-dimensional porous carbon skeleton.
Drawings
FIG. 1 is a scanning electron microscope image of a Co-MOF/C composite material prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the Co-Ni-OH/C composite material prepared in example 1 of the present invention;
FIG. 3 is an X-ray diffraction pattern of a dual three-dimensional porous Ni-Co-Se/C composite material prepared in examples 1,2, and 3 of the present invention;
FIG. 4 is a Raman spectrum of the three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the present invention;
FIG. 5 is a low power scanning electron microscope image of the three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the present invention;
FIG. 6 is a high power scanning electron microscope image of the three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the present invention;
FIG. 7 is a transmission electron microscope image of a three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the present invention;
FIG. 8 is a high resolution transmission electron microscope image of a three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the present invention, with an illustration of a selected area electron diffraction pattern;
FIG. 9 is an X-ray photoelectron spectrum of a three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the present invention: (a) a full spectrum, (b) a Ni 2p high resolution spectrum, (C) a Co 2p high resolution spectrum, (d) a Se 3p high resolution spectrum, (e) a C1 s high resolution spectrum, (f) an N1s high resolution spectrum;
FIG. 10 is a cyclic voltammogram of the three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the invention as an electrode material of a supercapacitor at different sweeping speeds;
FIG. 11 is a constant current charge-discharge diagram of the three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the present invention under different current densities as an electrode material of a supercapacitor;
FIG. 12 is a cyclic voltammogram of different voltages of a double three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the invention as a two-electrode asymmetric supercapacitor electrode material;
FIG. 13 is a cyclic voltammogram of the three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the invention as electrode material of a two-electrode asymmetric supercapacitor at different sweep rates;
FIG. 14 is a schematic diagram showing a three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the present invention as a two-electrode asymmetric supercapacitor electrode material 10A g -1 Cycle performance at current density;
FIG. 15 is a schematic illustration of an LED lamp lit by using the three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 as a two-electrode asymmetric supercapacitor;
FIG. 16 is a scanning electron microscope image of a three-dimensional porous Ni-Co-Se/C composite material prepared in example 2 of the present invention;
FIG. 17 is a cyclic voltammogram of the three-dimensional porous Ni-Co-Se/C composite material prepared in example 2 of the present invention as an electrode material of a supercapacitor at different sweep rates;
FIG. 18 is a constant current charge-discharge diagram of the three-dimensional porous Ni-Co-Se/C composite material prepared in example 2 of the present invention under different current densities as an electrode material of a supercapacitor;
FIG. 19 is a scanning electron microscope image of a three-dimensional porous Ni-Co-Se/C composite material prepared in example 3 of the present invention;
FIG. 20 is a cyclic voltammogram of the three-dimensional porous Ni-Co-Se/C composite material prepared in example 3 of the invention as an electrode material of a supercapacitor at different sweeping speeds;
FIG. 21 is a constant current charge-discharge diagram of the three-dimensional porous Ni-Co-Se/C composite material prepared in example 3 of the present invention under different current densities as an electrode material of a supercapacitor;
FIG. 22 is a scanning electron microscope image of a three-dimensional porous Ni-Co-Se/C composite material prepared in example 4 of the present invention;
FIG. 23 is a scanning electron microscope image of a three-dimensional porous Ni-Co-Se/C composite material prepared in example 5 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and examples, but the present invention is not limited to the following examples.
Example 1
A bimetal selenide-porous carbon composite material for a super capacitor comprises the following specific steps:
(1) 30mL of a 0.4 mol/L2-methylimidazole solution and 30mL of a 0.05 mol/L cobalt nitrate solution were prepared, respectively; under the stirring condition, pouring a cobalt nitrate solution into a 2-methylimidazole solution, placing the mixed solution in a microwave oven for 20 seconds, immersing hydrophilically treated butterfly wing-derived carbon (acid soaking treatment, increasing oxygen-containing groups on the surface of a sample) into the solution, standing and growing for 25 minutes, taking out, washing and drying to obtain Co-MOF which uniformly grows on a porous carbon skeleton, and marking as Co-MOF/C;
(2) Immersing the dried product of step (1) into 1 mmol ∙ L -1 Soaking in ethanol solution of nickel nitrate for 5 min, taking out, drying to obtain cobalt nickel hydroxide, growing on carbonized butterfly wings, and marking as Ni-Co-OH/C;
(3) Adding sodium selenite into deionized water of 14 mL, stirring and dissolving fully to obtain 8-9 mmol/L sodium selenite solution, adding hydrazine hydrate of 0.5 mL to make the concentration of the solution be 1.1 mmol/L, immersing Ni-Co-OH/C in the step (2), transferring the immersed Ni-Co-OH/C into a hydrothermal reaction kettle, reacting at 160 ℃ for 6 h, naturally cooling, washing and drying to obtain the three-dimensional porous Ni-Co-Se/C-160 composite material.
It can be seen from fig. 1 that the prepared butterfly wing derived carbon surface grows a uniformly arranged two-dimensional nano Co-MOF array, under the microwave condition, the two-dimensional Co-MOF nano sheet presents a unique long sword-shaped structure and grows along the carbon ridge array, and a regular and orderly parallel array is obtained, and the thickness of the Co-MOF sheet is about 150 nm.
As can be seen from FIG. 2, the prepared butterfly wing-derived carbon surface grows a two-dimensional nano Co-MOF array which is uniformly arranged, and the obtained Ni-Co-OH keeps the lamellar array structure of the Co-MOF through ion exchange reaction with nickel nitrate, but the whole lamellar structure slightly shrinks and sags on the carbon surface, and the lamellar thickness is about 90 nm.
As can be seen from FIG. 3, the X-ray diffraction (XRD) pattern of the prepared three-dimensional porous Ni-Co-Se/C-160 composite material shows the materialThe peak shape of (C) corresponds to (Co, ni) 0.85 Standard peaks of Se and characteristic peaks of carbon, indicating that the synthesized product is (Co, ni) 0.85 Se/C composite materials.
From FIG. 4, it can be seen that the Raman spectrum of the prepared three-dimensional porous Ni-Co-Se/C-160 composite material shows 1359 and 1359 cm -1 And 1591 cm -1 At two characteristic peaks, respectively belonging to sp 3 And sp (sp) 2 D-band (disordered carbon) and G-band (graphitic carbon) of bonded carbons. Fitting calculation shows that the intensity of the D peak and the G peakI D /I G ) About 0.86, indicating that the butterfly wing derived carbon is predominantly amorphous carbon. At 179.9, 452.1, 485.9 and 647.4 cm -1 The raman peaks at are respectively attributed to Co 0.85 Se and Ni 0.85 A of Se g 、E g 、F 2g And A 1g 。
From fig. 5 and fig. 6, it can be seen that the scanning image of the prepared three-dimensional porous Ni-Co-Se/C-160 composite material shows that the original surface-grown sword-like sheet structure has been decomposed in situ to become compact nano sheets, the nano sheets are densely and uniformly grown on a carbon skeleton, a small amount of semitransparent thin sheets fall between ridge arrays, and the original three-dimensional porous carbon skeleton is clearly visible.
From fig. 7, it can be seen that a Transmission Electron Microscope (TEM) image of the prepared Ni-Co-Se nano-sheet demonstrates that the Ni-Co-Se grown on the surface of the three-dimensional carbon skeleton is a sheet structure, the thickness is thin, the wrinkled texture appears, and the unique two-dimensional nano-sheet structure can combine the size effect and the structural advantage to provide more redox sites.
From fig. 8, it can be seen that the High Resolution Transmission Electron Microscope (HRTEM) picture of the prepared Ni-Co-Se nano-sheet, and the electron diffraction in the inset can see a continuous diffraction ring, indicating that the nano-sheet has polycrystalline characteristics. The HRTEM image can clearly see criss-cross lattice stripes, and the lattice spacing is determined to be 0.27-nm through measurement, and Co 0.85 Se (JCPDS No. 52-1008) and Ni 0.85 The (101) crystal planes of Se (JCPDS No. 18-0888) are matched.
From FIG. 9, it can be seen that the prepared three-dimensional porous Ni-Co-Se/C-160 composite material has X-ray photoelectron spectroscopy (XPS).
Fig. 9 (a) shows the presence of Co, ni, C, N and Se elements in the composite.
FIG. 9 (b) is a Ni 2p spectrum, divided into 4 individual peaks, corresponding to two spin orbit peaks and two satellite peaks, two peaks at binding energies 873.8 and 856.1 eV corresponding to Ni 3+ Ni 2p of (2) 1/2 And Ni 2p 3/2 The two peaks at 881.0 and 863.1 eV are satellite peaks.
FIG. 9 (c) is a Co 2p spectrum, characteristic peaks at 781.0 and 796.9 eV correspond to Co 2p 3/2 And Co 2p 1/2 The energy difference between these two peaks (δe=15.9 eV) demonstrates Co for the rail 2+ Is present. The remaining two peaks at 785.7 and 802.7 eV are Co 2+ Is a satellite peak of (2).
FIG. 9 (d) is a spectrum of Se 3p showing that Se has a multivalent state, and three peaks at 55.6, 59.1 and 60.5, eV can be fitted, corresponding to Se 3d 5/2 Rail, se 3d 3/2 Orbitals and Se-O bonds.
Fig. 9 (e) is a C1 s spectrum, with three peaks at 284.8, 286.8 and 290.4 eV corresponding to C-C, C-N and c=o bonds, respectively.
Fig. 9 (f) is a plot of N1s, with peaks at 399.1, 399.7 and 400.8 eV corresponding to pyridine nitrogen, pyrrole nitrogen and graphite nitrogen, respectively, demonstrating that the carbon matrix is doped with nitrogen heteroatoms.
From FIG. 10, it can be seen that the prepared three-dimensional porous Ni-Co-Se/C-160 composite material was used as a three-electrode supercapacitor (electrochemical behavior of supercapacitor electrode was performed using CHI 660E electrochemical workstation (Shanghai morning bloom) in a standard three-electrode system. 6 mol ∙ L was used -1 Wherein Ni-Co-Se/C-160 is used as a working electrode, hg/HgO and Pt foil electrode are used as a reference electrode and a counter electrode, respectively. For the development measurement, the Ni-Co-Se/C-160 working electrode was sandwiched between two sheets of foamed nickel (1 cm X1 cm) as a conductive carrier. ) The Cyclic Voltammetry (CV) curve of (C) shows a pair of redox peaks indicating that Ni-Co-Se undergoes a reversible Faraday redox reaction associated with pseudocapacitance. The redox mechanism and process of Ni-Co-Se involves Co 2+ /Co 3+ /Co 4+ And Ni 2+ /Ni 3+ And (3) converting. As the scan rate increases, the position of the anode and cathode peaks moves toward both ends of the voltage, the peak current increases linearly due to OH in the alkaline electrolyte - Insufficient insertion of Ni-Co-Se.
As can be seen from FIG. 11, the prepared three-dimensional porous Ni-Co-Se/C-160 composite material is used as a three-electrode supercapacitor at different current densities (1-20A ∙ g -1 ) Under this, the plateau region apparent in the constant current charge/discharge (GCD) curve is very coincident with the relevant redox peak in the CV curve. At the same time, the GCD curve shows near symmetry and a small internal resistance drop, indicating its excellent reversibility and faster reaction kinetics. In addition, the results show that the three-dimensional porous Ni-Co-Se/C composite material has excellent multiplying power performance, and the multiplying power performance is 1 g/A ∙ g -1 Specific time capacity of 3013.7F ∙ g -1 At 20A ∙ g -1 Is kept at 936.3F ∙ g -1 。
From FIG. 12, it can be seen that the asymmetric supercapacitor consisting of the three-dimensional porous Ni-Co-Se/C-160 composite material and activated butterfly wing carbon was at 6 mol ∙ L -1 In the KOH aqueous electrolyte, at 50 mV ∙ s -1 CV curves for different voltage ranges. It is apparent that polarization occurs at 1.7V and the voltage can be determined to be 1.6V.
The CV curves of the asymmetric supercapacitor consisting of the three-dimensional porous Ni-Co-Se/C-160 composite material and the activated butterfly wing carbon under different scanning rates and potential windows of 0-1.6V can be seen from the graph 13. The results show that the asymmetric supercapacitor has the characteristics of a mixture of a battery and an electric double layer capacitor.
The charge-discharge diagram of the asymmetric supercapacitor consisting of the three-dimensional porous Ni-Co-Se/C-160 composite material and the activated butterfly wing carbon under the potential window of 0-1.6V can be seen in FIG. 14, and the electrode at 1A ∙ g can be calculated according to the charge-discharge diagram -1 Specific capacity at time 139.8 g F ∙ g -1 At 10A g -1 When it reaches 54.3 Fg -1 。
From FIG. 15, it can be seen that the cycle diagram of the asymmetric supercapacitor composed of the three-dimensional porous Ni-Co-Se/C-160 composite material and activated butterfly wing carbon under the potential window of 0-1.6V has the current density of 10 A g -1 When the capacitor shows excellent cycle stability, after 5000 times of continuous cycle, the specific capacity is still 93.3% of the initial capacitance, and the long-term cycle stability is proved. In the illustration, the asymmetric supercapacitor assembled by two electrodes is used for lighting the LED lamp of 2V, so that the practical value of the LED lamp is proved.
Example 2
Example 1 was repeated except that the hydrothermal selenization temperature in step 3 was 140 ℃.
From FIG. 3, it can be seen that the X-ray diffraction (XRD) pattern of the three-dimensional porous bimetallic selenide/carbon (Ni-Co-Se/C-140) composite material prepared at 140 ℃ shows that the peak shape of the material is the same as that of the three-dimensional porous Ni-Co-Se/C-160 composite material of example 1, indicating that the synthesized cobalt-nickel selenide crystal structure remains unchanged.
From fig. 16, it can be seen that SEM images of the prepared three-dimensional porous Ni-Co-Se/C-140 composite material show that the bi-metal selenide is not firmly grown on the three-dimensional porous carbon skeleton, but rather loosely grown on the three-dimensional porous carbon skeleton.
It can be seen from FIG. 17 that the CV curve of the prepared three-dimensional porous Ni-Co-Se/C-140 composite material used as a three-electrode supercapacitor was similar to that of example 1, and also shows a pair of redox peaks indicating that Ni-Co-Se developed reversible Faraday redox reactions associated with pseudocapacitance. The redox mechanism and process involves Co 2+ /Co 3+ /Co 4+ And Ni 2+ /Ni 3+ And (3) converting. As the scan rate increases, the position of the anode and cathode peaks moves toward both ends of the voltage, and the peak current increases linearly.
As can be seen from FIG. 18, the prepared three-dimensional porous Ni-Co-Se/C-140 composite material is used as a three-electrode supercapacitor at different current densities (1-20A ∙ g) -1 ) Under this, the plateau region apparent in the constant current charge/discharge (GCD) curve is very coincident with the relevant redox peak in the CV curve. The results show that the specific capacity and rate capability of the three-dimensional porous Ni-Co-Se/C-140 composite material are inferior to those of the three-dimensional porous Ni-Co-Se/C-160 composite material.
Example 3
Example 1 was repeated except that the hydrothermal selenization temperature in step 3 was 180 ℃.
From fig. 1, it can be seen that the X-ray diffraction (XRD) pattern of the three-dimensional porous bi-metal selenide/carbon (Ni-Co-Se/C-180) composite material prepared at 180 ℃ showed that the peak shape of the material was the same as that of the three-dimensional porous bi-metal selenide/carbon composite materials of examples 1 and 2, indicating that the synthesized cobalt nickel selenide crystal structure remained unchanged.
From fig. 19, it can be seen that SEM images of the prepared three-dimensional porous Ni-Co-Se/C-180 composite material show that the bi-metal selenide is not grown on the three-dimensional porous carbon skeleton in a two-dimensional sheet structure, but a large number of particles are closely packed on the three-dimensional porous carbon skeleton.
It can be seen from FIG. 20 that the CV curve of the prepared three-dimensional porous Ni-Co-Se/C-180 composite material used as a three-electrode supercapacitor was similar to that in examples 1 and 2, and also showed a pair of redox peaks indicating reversible Faraday redox reactions associated with pseudocapacitive Ni-Co-Se. The redox mechanism and process involves Co 2+ /Co 3+ /Co 4+ And Ni 2+ /Ni 3+ And (3) converting. As the scan rate increases, the position of the anode and cathode peaks moves toward both ends of the voltage, and the peak current increases linearly.
As can be seen from FIG. 21, the prepared three-dimensional porous Ni-Co-Se/C-180 composite material is used as a three-electrode supercapacitor with different current densities (1-20A ∙ g) -1 ) Under this, the plateau region apparent in the constant current charge/discharge (GCD) curve is very coincident with the relevant redox peak in the CV curve. The results show that the specific capacity and rate capability of the three-dimensional porous Ni-Co-Se/C-180 composite material are inferior to those of the three-dimensional porous Ni-Co-Se/C-160 composite material, but superior to those of the three-dimensional porous Ni-Co-Se/C-140 composite material.
Example 4
The difference from example 1 is that the concentration of cobalt nitrate is 0.04 mol/L. The resulting material is shown in fig. 22, and the SEM image shows the resulting fluffy nanostructure stacked on a three-dimensional carbon skeleton, compared to case 1.
Example 5
The difference from example 1 is that the concentration of cobalt nitrate is 0.06 mol/L. The resulting material is shown in fig. 23, and SEM images show that the resulting sheet-like structure is sparse and no ultrathin structure is found, as compared to case 1.
The invention adopts microwave treatment-ion exchange-chemical etching-hydrothermal selenizing technology design to prepare the Co-Ni-Se nano sheet uniformly grown on the three-dimensional porous carbon skeleton. Thanks to its multicomponent and unique structure, co-Ni-Se/C-160 exhibits excellent supercapacitor performance as a self-supporting electrode, which can be explained by the ordered pore array ensuring sufficient wetting between the electrolyte and the electrode material, co-Ni-Se nanoplatelets can expose more active sites. In addition, the unique structure enables the ion/electron transfer and diffusion between the three-dimensional porous carbon skeleton and the Ni-Co-Se to be more effective, so that the electrochemical reaction kinetics are effectively accelerated, and the reasonable design of electrode materials is important for adjusting the electrochemical performance of the advanced energy storage system.
In addition to the above embodiments, other embodiments of the present invention are possible, and all technical solutions formed by equivalent substitution or equivalent transformation are within the scope of the present invention.
Claims (5)
1. The preparation method of the bimetal selenide-porous carbon composite material for the super capacitor is characterized by comprising the following specific steps of:
step 1, respectively preparing a 2-methylimidazole solution and a cobalt nitrate solution, pouring the cobalt nitrate solution into the 2-methylimidazole solution under a stirring state to obtain a mixed solution, placing the mixed solution into a microwave oven for treatment, immersing a three-dimensional porous carbon skeleton which is used as a substrate and is subjected to hydrophilic treatment into the mixed solution for reaction for 25 minutes, taking out, washing and drying to obtain Co-MOF which uniformly grows on the porous carbon skeleton and is recorded as Co-MOF/C, wherein the three-dimensional porous carbon skeleton is derived from a butterfly wing derived carbonized material;
step 2, immersing Co-MOF/C into an ethanol solution of nickel nitrate to obtain cobalt nickel hydroxide which grows on a three-dimensional porous carbon skeleton and is marked as Ni-Co-OH/C;
preparing sodium selenite solution, adding hydrazine hydrate to enable the concentration of the sodium selenite solution to be 1.1 mmol/L, immersing the Ni-Co-OH/C prepared in the step 2 into the solution, transferring the solution into a hydrothermal reaction kettle to react at 140-180 ℃, naturally cooling the reaction product, taking out the product, washing and drying the product to obtain a porous carbon loaded cobalt-nickel selenide composite material, and marking the porous carbon loaded cobalt-nickel selenide composite material as Ni-Co-Se/C, wherein the concentration of the sodium selenite is 8-9 mmol/L in the hydrothermal selenizing process.
2. The method for preparing the bimetal selenide-porous carbon composite for the super capacitor of claim 1, wherein the concentration of cobalt nitrate is 0.04-0.06 mol/L, the concentration of 2-methylimidazole is 0.4 mol/L, the concentration of nickel nitrate is 1 mmol/L, and the concentration of sodium selenite is 8-9 mmol/L.
3. The method for preparing a bimetal selenide-porous carbon composite for a super capacitor according to claim 1, wherein the step 2 is to soak the Co-MOFs/C in 1 mmol/L nickel nitrate ethanol solution for 5 minutes.
4. A bi-metal selenide-porous carbon composite prepared based on the method of claims 1-3.
5. Use of a bi-metal selenide-porous carbon composite according to claim 4 for the preparation of a supercapacitor.
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