CN114783786A - 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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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 46
- 239000003990 capacitor Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 15
- 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
- PYHYDDIOBZRCJU-UHFFFAOYSA-N [Ni]=[Se].[Co] Chemical compound [Ni]=[Se].[Co] PYHYDDIOBZRCJU-UHFFFAOYSA-N 0.000 claims abstract description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract 6
- 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 28
- 244000241796 Christia obcordata Species 0.000 claims description 12
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 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 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 5
- 229960001471 sodium selenite Drugs 0.000 claims description 5
- 235000015921 sodium selenite Nutrition 0.000 claims description 5
- 239000011781 sodium selenite Substances 0.000 claims description 5
- 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 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 235000010288 sodium nitrite Nutrition 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000005539 carbonized material Substances 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 8
- 239000013543 active substance Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000002135 nanosheet Substances 0.000 description 16
- 238000002484 cyclic voltammetry Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000001000 micrograph Methods 0.000 description 10
- 150000004771 selenides Chemical class 0.000 description 7
- 230000001351 cycling effect Effects 0.000 description 6
- 238000006479 redox reaction Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- -1 transition metal chalcogenide Chemical class 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000003491 array Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 238000001069 Raman spectroscopy Methods 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000013384 organic framework Substances 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
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- 239000011148 porous material Substances 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
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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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 and a preparation method and application thereof are disclosed, wherein an activated three-dimensional porous carbon skeleton is taken as a substrate material, cobalt nitrate and 2-methylimidazole react on the surface of the carbon skeleton, and Co-MOF uniformly grows on the porous carbon skeleton; then immersing the carbon skeleton in a nickel nitrate ethanol solution to prepare cobalt nickel hydroxide to grow on the carbon skeleton; and then preparing the porous carbon loaded cobalt nickel selenide composite material 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 when being used as a super capacitor electrode material, and 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 bimetallic selenide-porous carbon composite material for a super capacitor and a preparation method and application thereof, belonging to the technical field of new materials.
Background
To achieve the goals of carbon peaking and carbon neutralization, efforts have been directed to developing clean and renewable energy conversion and storage systems, such as Supercapacitors (SCs), Lithium Ion Batteries (LIBs), and the like. Lithium ion batteries and super capacitors in energy storage devices are hot spots for research by virtue of respective advantages. The super capacitor is used as a novel energy storage device and 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, the transition metal chalcogenide has become a feasible substitute of the graphite bifunctional electrode material in the super capacitor due to the characteristics of large theoretical specific capacity and various valence statesEnergy Stor. Mater. 2020, 31, 252.]. The transition metal selenides have higher ion diffusion kinetics (1 × 10) than the corresponding oxides and sulfides-5 S∙m-1) And higher electrode conductivity (1X 10)-3 S∙m-1) This facilitates stable and reliable operation in the supercapacitorNano Res. 2021, 14, 896-896.]. For example, SnSe nanosheets prepared by liquid phase techniques were at 0.5A ∙ g-1Has a molecular weight of 228F ∙ g-1 At 10A ∙ g-1Has a molecular weight of 117F ∙ g-1In the range of 1.0A ∙ g-199.0% initial capacity retention rate after the next 1000 cyclesACS Nano, 2014, 8, 3761-3770.]. Zinc Cobalt Selenide (ZCS) as a battery type superElectrode material for secondary capacitors, in the range of 2A ∙ g-1Has a molecular weight of 1419C ∙ g-1And the ZCS// AC battery-supercapacitor hybrid device realizes a wide potential window of 1.6V and 77.78 Wh kg-1And a high specific energy of 222W ∙ kg-1The initial capacity retention rate after 10000 cycles is still as high as 80%J. Energy Storage, 2020, 31: 101663.]. However, the transition metal selenide electrode material faces problems of low conductivity, slow ion/electron transport kinetics, and low cycling stability, which prevents its practical applicationChem. Eng. J., 2019, 364, 320.]。
In view of the above-mentioned problems to be solved, reasonable structural design and composite engineering are feasible 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. By utilizing the unique hierarchical structure and the synergistic effect of the bimetallic selenide, the three-dimensional porous Ni-Co-Se/C composite material as the electrode material of the super capacitor shows excellent multiplying power and cycle performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the bimetallic selenide-porous carbon composite material for the super capacitor and the preparation method and the application thereof. In addition, the unique structure enables ion/electron transfer and diffusion between the three-dimensional porous carbon skeleton and the Ni-Co-Se to be more effective, and effectively accelerates the electrochemical reaction kinetics. The Ni-Co-Se/C composite material is applied to the super capacitor and has excellent multiplying power and cycling stability.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
a bimetal selenide-porous carbon composite material for a super capacitor comprises the following specific steps:
and 3, preparing a sodium nitrite solution, adding 1.1 mmol/L hydrazine hydrate to enable the concentration of the sodium nitrite 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, taking out a product, washing and drying to obtain the porous carbon loaded cobalt nickel selenide composite material, and marking the porous carbon loaded cobalt nickel selenide composite material as Ni-Co-Se/C.
As an improvement, the three-dimensional porous carbon skeleton comes from butterfly wing derivative carbonized materials.
The improved method is characterized in that 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.
Has the beneficial effects that:
compared with the prior art, the bimetallic selenide-porous carbon composite material for the super capacitor, and the preparation method and the application thereof have the following advantages:
(1) the cobalt nickel selenide nanosheet growing on the butterfly wing-derived three-dimensional porous carbon skeleton is prepared through microwave precipitation, ion exchange and hydrothermal selenization technologies. In the preparation process, the ligand of the Co-MOF can be uniformly removed, and a metal center is left to be combined with hydroxide ions in the solution, so that a Co-Ni-OH intermediate is obtained; and then selenizing, wherein most of the product inherits the structural characteristics of the Co-Ni-OH nanosheets, and part of the ultrathin nanosheets are obtained by 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 the MOF grown on the carbon skeleton provides uniform and limited 'metal seeds', a two-dimensional nanosheet structure is formed, volume expansion can be relieved, the electron transfer rate is facilitated, and the number of active sites is increased; the Ni-Co-Se nanosheets are uniformly and firmly anchored on the three-dimensional carbon skeleton, and can prevent the active materials from agglomerating and falling off, so that the structural stability is effectively improved. The unique multilevel structure and the synergistic effect of the bimetallic selenide enable the material to show excellent cycling stability and rate capability when applied to a super capacitor;
(2) the carbon source adopted by the invention is butterfly wing derived carbon, the natural three-dimensional ordered porous structure has the advantages of environmental friendliness, wide source, low price and easy obtainment and the like, and the cobalt nickel selenide nanosheets grown on the three-dimensional porous carbon skeleton are prepared by combining room-temperature deposition self-assembly, ion exchange and hydrothermal selenization technologies.
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 spectrum 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 a three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the present invention;
FIG. 5 is a scanning electron microscope image of a 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 prepared in example 1 of the present invention;
FIG. 8 is a high resolution transmission electron microscope image of the three-dimensional porous Ni-Co-Se/C composite prepared in example 1 of the present invention, with the inset showing the 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 spectrogram, (b) a Ni 2p high-resolution spectrogram, (C) a Co 2p high-resolution spectrogram, (d) a Se 3p high-resolution spectrogram, (e) a C1 s high-resolution spectrogram, and (f) an N1s high-resolution spectrogram;
FIG. 10 is a cyclic voltammogram of the three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the present invention as the supercapacitor electrode material at different sweep rates;
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 as the electrode material of a supercapacitor at different current densities;
FIG. 12 is a cyclic voltammogram of different voltages of a two-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the present invention as an asymmetric supercapacitor electrode material with two electrodes;
FIG. 13 is a cyclic voltammogram of the three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the present invention as the electrode material of the two-electrode asymmetric supercapacitor at different sweep rates;
FIG. 14 shows that the three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the invention is used as a two-electrode asymmetric supercapacitor electrode material 10A g-1Cycling performance at current density;
FIG. 15 is a drawing of a three-dimensional porous Ni-Co-Se/C composite material prepared in example 1 of the present invention as a two-electrode asymmetric supercapacitor illuminated LED lamp;
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 a supercapacitor electrode material 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 as the electrode material of a supercapacitor at different current densities;
FIG. 19 is a scanning electron microscope image of a three-dimensional porous Ni-Co-Se/C composite 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 present invention as a supercapacitor electrode material at different sweep rates;
FIG. 21 is a constant current charge and discharge plot at different current densities for the three-dimensional porous Ni-Co-Se/C composite material prepared in example 3 of the present invention as the electrode material of a supercapacitor;
FIG. 22 is a scanning electron microscope image of a three-dimensional porous Ni-Co-Se/C composite 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 prepared in example 5 of the present invention.
Detailed Description
The present invention will be further described with reference to the drawings and examples, but the present invention is not limited to the examples.
Example 1
A bimetal selenide-porous carbon composite material for a super capacitor comprises the following specific steps:
(1) respectively preparing 30mL of 0.4 mol/L2-methylimidazole solution and 30mL of 0.05 mol/L cobalt nitrate solution; pouring a cobalt nitrate solution into a 2-methylimidazole solution under a stirring condition, placing the mixed solution in a microwave oven for 20 seconds, then immersing the carbon derived from the butterfly wings subjected to hydrophilic treatment (acid bubble treatment for increasing oxygen-containing groups on the surface of a sample) into the solution, standing for growth for 25 minutes, taking out, washing and drying to obtain Co-MOF (cobalt-organic framework) uniformly growing on a porous carbon skeleton, and marking as Co-MOF/C;
(2) immersing the dried product of the step (1) into 1 mmol ∙ L-1Soaking the nickel nitrate in ethanol solution for 5 minutes, taking out the nickel nitrate, and drying to obtain cobalt nickel hydroxide growing on the carbonized butterfly wing, wherein the cobalt nickel hydroxide is marked as Ni-Co-OH/C;
(3) adding sodium selenite into 14 mL of deionized water, fully stirring and dissolving to obtain 8-9 mmol/L sodium selenite solution, adding 0.5 mL of hydrazine hydrate to enable the concentration of the hydrazine hydrate to 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 for 6 hours at 160 ℃, naturally cooling, washing and drying to obtain the three-dimensional porous Ni-Co-Se/C-160 composite material.
As can be seen from figure 1, two-dimensional nano Co-MOF arrays which are uniformly arranged grow on the surface of the prepared butterfly wing derived carbon, under the microwave condition, the two-dimensional Co-MOF nanosheets have unique long sword-shaped structures and grow along the arrangement of carbon ridges to obtain regular and ordered parallel arrays, and the thickness of the Co-MOF sheets is about 150 nm.
As can be seen from figure 2, two-dimensional nano Co-MOF arrays which are uniformly arranged grow on the surface of the prepared butterfly wing derived carbon, and the Ni-Co-OH obtained through ion exchange reaction with nickel nitrate keeps the lamellar array structure of the Co-MOF, but the whole lamellar structure slightly shrinks and sinks on the surface of the carbon, and the lamellar thickness is about 90 nm.
It can be seen from FIG. 3 that the X-ray diffraction (XRD) pattern of the prepared three-dimensional porous Ni-Co-Se/C-160 composite material shows that the peak shape of the material corresponds to (Co, Ni)0.85Standard peak of Se and characteristic peak of carbon, indicating that the synthesized product is (Co, Ni)0.85Se/C composite material.
It can be seen from FIG. 4 that the Raman spectrum of the prepared three-dimensional porous Ni-Co-Se/C-160 composite material exhibits 1359 cm-1And 1591 cm-1Two characteristic peaks, respectively belonging to sp3And sp2Carbon-bonded D bands (disordered carbon) and G bands (graphitic carbon). Fitting calculation shows intensities of D and G peaks: (I D/I G) About 0.86, indicating that the pteroid-derived carbon is predominantly amorphous carbon. At 179.9, 452.1, 485.9 and 647.4 cm-1The Raman peaks at (A) are respectively attributed to Co0.85Se and Ni0.85A of Seg、Eg、F2gAnd A1g。
From the scanned images of the prepared three-dimensional porous Ni-Co-Se/C-160 composite material shown in FIGS. 5 and 6, it can be seen that the original sword-shaped sheet structure growing on the surface has been decomposed in situ to become dense nanosheets, the nanosheets grow densely and uniformly on the carbon skeleton, a small number of semi-transparent flakes fall between the ridge arrays, and the original three-dimensional porous carbon skeleton is clear and visible.
From FIG. 7, it can be seen that a Transmission Electron Microscope (TEM) image of the prepared Ni-Co-Se nanosheet proves that the Ni-Co-Se grown on the surface of the three-dimensional carbon skeleton is of a sheet structure, the thickness of the Ni-Co-Se is thinner, a wrinkled texture appears, and the unique two-dimensional nanosheet structure can combine the size effect and the structural advantages 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 nanosheet, the electron diffraction in the inset can see the continuous diffraction ring, indicating that the nanosheet has the polycrystalline characteristics. HRTEM image can clearly see criss-cross lattice fringes, and the lattice spacing is determined to be-0.27 nm through measurement, and the lattice fringes are matched with Co0.85Se (JCPDS No. 52-1008) and Ni0.85The (101) crystal face of Se (JCPDS No. 18-0888) is matched.
From FIG. 9, X-ray photoelectron spectroscopy (XPS) of the prepared three-dimensional porous Ni-Co-Se/C-160 composite material can be seen.
Fig. 9 (a) shows the presence of Co, Ni, C, N and Se elements in the composite material.
FIG. 9(b) is a Ni 2p spectrum, divided into 4 separate peaks, corresponding to two spin orbit doublets and two satellite peaks, with two peaks at binding energies of 873.8 and 856.1 eV corresponding to Ni3+Ni 2p of1/2And Ni 2p3/2In orbit, the two peaks at 881.0 and 863.1 eV are satellite peaks.
FIG. 9(c) is a spectrum of Co 2p, with characteristic peaks at 781.0 and 796.9 eV corresponding to Co 2p3/2And Co 2p1/2Orbitals, the energy difference between these two peaks (δ E =15.9 eV) evidences Co2+Is present. The remaining two peaks at 785.7 and 802.7 eV are Co2+The satellite peak of (a).
FIG. 9(d) is a spectrum of Se 3p showing that Se has multiple valence states and can be fit to three peaks at 55.6, 59.1 and 60.5 eV, corresponding to Se 3d5/2Track, Se 3d3/2Orbital and Se-O bond.
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 spectrum 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.
It can be seen from FIG. 10 that the prepared three-dimensional porous Ni-Co-Se/C-160 composite material is used as a three-electrode supercapacitor (electrochemical behavior of supercapacitor electrodes is performed in a standard three-electrode system using CHI 660E electrochemical workstation (Shanghai morning Hua.) 6 mol ∙ L is used-1With Ni-Co-Se/C-160 as the working electrode and Hg/HgO and Pt foil electrodes as the reference and counter electrodes, respectively. For the development of the measurement, the Ni-Co-Se/C-160 working electrode was sandwiched between two pieces of nickel foam (1 cm. times.1 cm) as a conductive support. ) The Cyclic Voltammetry (CV) curve of (a) shows a pair of redox peaks indicating that Ni-Co-Se undergoes a reversible faradaic redox reaction associated with pseudocapacitance. The redox reaction mechanism and process of Ni-Co-Se involves Co2+/Co3+/Co4+And Ni2+/Ni3+And (4) converting. As the scan rate increases, the position of the anode and cathode peaks move across the voltage and the peak current increases linearly due to OH in the alkaline electrolyte-Insufficient insertion of Ni-Co-Se.
FIG. 11 shows that 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) Next, the apparent plateau region in the constant current charge/discharge (GCD) curve is very consistent with the associated redox peak in the CV curve. At the same time, the GCD curve shows near symmetry and less 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 rate performance, and the rate performance is 1A ∙ g-1The specific capacity is 3013.7F ∙ g-1At 20A ∙ g-1It is still maintained at 936.3F ∙ g-1。
From FIG. 12, it can be seen that the asymmetric supercapacitor made of the three-dimensional porous Ni-Co-Se/C-160 composite material and the activated butterfly wing carbon is 6 mol ∙ L-1In KOH aqueous electrolyte, at 50 mV ∙ s-1CV curves for different voltage ranges. Obviously, polarization occurs at 17V, the voltage can be determined to be 1.6V.
FIG. 13 shows CV curves of an asymmetric supercapacitor made of the three-dimensional porous Ni-Co-Se/C-160 composite material and activated butterfly wing carbon under different scanning rates and a potential window of 0-1.6V. The results show that the asymmetric supercapacitor has a hybrid characteristic of battery and electric double layer type capacitance.
FIG. 14 shows the charge-discharge diagram of the asymmetric supercapacitor made 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, and the charge-discharge diagram can be used for calculating the potential of the electrode under 1A ∙ g-1The specific capacity at high temperature was 139.8F ∙ g-1At 10A g-1Then 54.3F g is reached-1。
FIG. 15 shows a cycle chart of an asymmetric supercapacitor composed of a three-dimensional porous Ni-Co-Se/C-160 composite material and activated butterfly wing carbon under a potential window of 0-1.6V, and the current density of the asymmetric supercapacitor is 10A g-1And (3) the high-performance lithium ion battery shows excellent cycling stability, and after 5000 times of continuous cycling, the specific capacity is still 93.3 percent of the initial capacitance, thereby proving the long-term cycling stability. In the inset, the 2V LED lamp is lighted by the asymmetrical super capacitor assembled by two electrodes, and the practical value is proved.
Example 2
The same procedure as in example 1 was repeated, except that the hydrothermal selenization temperature in step 3 was 140 ℃.
It can be seen from fig. 3 that the X-ray diffraction (XRD) pattern of the three-dimensional porous bimetal selenide/carbon (Ni-Co-Se/C-140) composite material prepared at 140 deg.c 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 crystal structure of the synthesized cobalt nickel selenide remains unchanged.
It can be seen from fig. 16 that SEM images of the prepared three-dimensional porous Ni-Co-Se/C-140 composite show that the bimetallic selenide is not strongly grown on the three-dimensional porous carbon skeleton, but loosely draped thereon.
It can be seen from FIG. 17 that the prepared three-dimensional porous Ni-Co-Se/C-140 composite material is used as a three-electrode super-capacitorThe CV curve of the vessel is similar to that of example 1 and also shows a pair of redox peaks indicating that Ni-Co-Se undergoes a reversible faradaic redox reaction associated with pseudocapacitance. Redox reaction mechanisms and processes involving Co2+/Co3+/Co4+And Ni2+/Ni3+And (4) converting. As the scan rate increases, the position of the anode and cathode peaks move towards the 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) Next, the apparent plateau region in the constant current charge/discharge (GCD) curve is very consistent with the associated redox peak in the CV curve. The result shows that the specific capacity and rate capability of the three-dimensional porous Ni-Co-Se/C-140 composite material are poorer than those of the three-dimensional porous Ni-Co-Se/C-160 composite material.
Example 3
The same as example 1 except that the hydrothermal selenization temperature in step 3 was 180 ℃.
It can be seen from fig. 1 that the X-ray diffraction (XRD) pattern of the three-dimensional porous bimetal selenide/carbon (Ni-Co-Se/C-180) composite material prepared at 180 deg.c shows that the peak shape of the material is the same as that of the three-dimensional porous bimetal selenide/carbon composite materials of examples 1 and 2, indicating that the crystal structure of the synthesized cobalt nickel selenide remains unchanged.
As can be seen from fig. 19, the SEM image of the prepared three-dimensional porous Ni-Co-Se/C-180 composite shows that the bimetallic selenide is not a two-dimensional sheet structure grown on the three-dimensional porous carbon skeleton, 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 curves of the prepared three-dimensional porous Ni-Co-Se/C-180 composite material used as a three-electrode supercapacitor are similar to those in examples 1 and 2, and also show a pair of redox peaks, representing reversible Faraday redox reactions associated with pseudocapacitance Ni-Co-Se. Redox reaction mechanisms and processes involving Co2+/Co3+/Co4+And Ni2+/Ni3+And (4) converting. With scanning rateAs the position of the anode and cathode peaks increases, moving towards the ends of the voltage, the peak current increases linearly.
FIG. 21 shows that the prepared three-dimensional porous Ni-Co-Se/C-180 composite material is used as a three-electrode supercapacitor at different current densities (1-20A ∙ g)-1) In the next place, the apparent plateau region in the constant current charge/discharge (GCD) curve is very consistent with the relevant redox peak in the CV curve. The result shows 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 was 0.04 mol/L. The resulting material is shown in fig. 22, and SEM images show that the resulting fluffy nanostructures are packed 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. As shown in fig. 23, the SEM image showed that the resulting sheet structure was sparse compared to case 1, and no ultra-thin structure was found.
The method adopts microwave treatment-ion exchange-chemical etching-hydrothermal selenization technology to design and prepare the Co-Ni-Se nanosheet uniformly grown on the three-dimensional porous carbon skeleton. Thanks to its multi-component and unique structure, Co-Ni-Se/C-160 as a self-supporting electrode shows excellent supercapacitor performance, which can be explained by the ordered pore array ensuring sufficient wetting between the electrolyte and the electrode material, and Co-Ni-Se nanosheets can expose more active sites. In addition, the unique structure enables ion/electron transfer and diffusion between the three-dimensional porous carbon skeleton and the Ni-Co-Se to be more effective, electrochemical reaction kinetics are effectively accelerated, and reasonable design of electrode materials is crucial to adjustment of electrochemical performance of an advanced energy storage system.
In addition to the above embodiments, the present invention may have other embodiments, and any technical solutions formed by equivalent substitutions or equivalent transformations are within the scope of the present invention.
Claims (7)
1. A preparation method of a bimetallic selenide-porous carbon composite material for a super capacitor is characterized by comprising 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 to obtain a mixed solution under a stirring state, placing the mixed solution into a microwave oven for treatment, immersing a three-dimensional porous carbon skeleton which serves as a substrate and is subjected to hydrophilic treatment into the mixed solution for reaction for 25 minutes, taking out the three-dimensional porous carbon skeleton, washing and drying the three-dimensional porous carbon skeleton, and uniformly growing Co-MOF on the porous carbon skeleton, wherein the Co-MOF/C is marked as Co-MOF;
step 2, immersing Co-MOF/C into an ethanol solution of nickel nitrate to obtain cobalt nickel hydroxide growing on the three-dimensional porous carbon skeleton, and marking as Ni-Co-OH/C;
and 3, preparing a sodium nitrite solution, adding 1.1 mmol/L hydrazine hydrate to enable the concentration of the sodium nitrite 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, taking out a product, washing and drying to obtain the porous carbon loaded cobalt nickel selenide composite material, and marking the porous carbon loaded cobalt nickel selenide composite material as Ni-Co-Se/C.
2. The method of claim 1, wherein the three-dimensional porous carbon skeleton is derived from a butterfly wing-derived carbonized material.
3. The method for preparing the bimetallic selenide-porous carbon composite material for the supercapacitor according to 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.
4. The method for preparing the bimetal selenide-porous carbon composite material for the supercapacitor according to claim 1, wherein the ion exchange process is to soak Co-MOFs/C in 1 mmol/L nickel nitrate ethanol solution for 5 minutes.
5. The method for preparing the bimetallic selenide-porous carbon composite material for the supercapacitor according to claim 1, wherein in the hydrothermal selenization process, the concentration of sodium selenite is 8-9 mmol/L.
6. The bimetallic selenide-porous carbon composite material prepared on the basis of the method of claims 1-5.
7. Use of the bimetallic selenide-porous carbon composite material according to claim 1 or claim 6 in the preparation of a supercapacitor.
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