CN115206686A - Method for preparing nickel-cobalt-zinc hydroxide/oxyhydroxide composite material by one-step method - Google Patents
Method for preparing nickel-cobalt-zinc hydroxide/oxyhydroxide composite material by one-step method Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 34
- FADXZUOQMVGNAC-UHFFFAOYSA-H zinc;cobalt(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2].[Zn+2] FADXZUOQMVGNAC-UHFFFAOYSA-H 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 26
- XYCQRIWVOKLIMW-UHFFFAOYSA-N [Co].[Ni].[Zn] Chemical compound [Co].[Ni].[Zn] XYCQRIWVOKLIMW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 238000004729 solvothermal method Methods 0.000 claims abstract description 12
- 239000003990 capacitor Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims abstract 2
- 239000002135 nanosheet Substances 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 230000009466 transformation Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000000224 chemical solution deposition Methods 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 abstract 1
- 229910020521 Co—Zn Inorganic materials 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- -1 nickel zinc nitrate hexahydrate Chemical compound 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
-
- 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
-
- 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
- H01G11/84—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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- 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
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention relates to the technical field of nano material preparation, and provides a method for preparing a nickel-cobalt-zinc hydroxide/oxyhydroxide composite material by a one-step method. The preparation method comprises the steps of carrying out ion exchange reaction on a mixed salt solution and a metal organic framework, and preparing the nickel-cobalt-zinc trimetal hydroxide/oxyhydroxide composite material in one step through a solvothermal process. The invention can effectively realize the phase control of the composite material by adjusting the thermal reaction time of the solvent, and does not need the subsequent chemical bath deposition conversion or electrochemical conversion procedure in the traditional preparation method. The composite material has a uniform hollow rhombic dodecahedron structure and obvious thin-layer nanosheets, and has high reactive sites and excellent electron transmission capability. The nickel-cobalt-zinc trimetal hydroxide/oxyhydroxide composite material provided by the invention is used for a super capacitor anode material, shows excellent specific capacity, rate capability and cycling stability, and has important significance in the field of electrochemistry.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a method for preparing a nickel-cobalt-zinc hydroxide/oxyhydroxide composite material in one step by utilizing solvothermal reaction and application thereof.
Background
The use of fossil fuels in large quantities does lead to rapid economic development, but also brings about global energy shortage and environmental pollution, so that the development, transformation and storage technology of new energy becomes the key point of technological breakthrough. In various different new energy devices, although the super capacitor is high in cost, high in technical difficulty and the like, the super capacitor is difficult to reach by other energy storage devices due to the ultrahigh power density and the excellent circulation stability, so that the super capacitor occupies an irreplaceable position in military industry or civilian population and becomes one of the most valuable research directions in the field of new energy. On the premise of keeping high power and long service life, the continuous breakthrough of the limit on energy density of the special energy storage device is still the main direction of the current technical development.
As a key part of the super capacitor, the electrode material greatly limits the exertion of the comprehensive performance of the super capacitor. Compared with a commercial low-capacity carbon electrode, the transition metal compound is a material with high electrochemical activity, high theoretical capacity and excellent conductivity, and particularly, a heterostructure containing heterogeneous anions is constructed in a reasonable mode, so that the respective advantages of all phases can be fully utilized, deep-level active sites are activated by a unique microscopic nano structure, the electron transfer and ion diffusion capacity is enhanced, the charge storage capacity is maximized, and the effect superior to that of a single phase is obtained. However, at present, the preparation of such composite materials usually requires a multi-step process to achieve phase transformation, i.e., firstly, a pure-phase material is prepared, and then, the pure-phase material is prepared through chemical bath deposition transformation or electrochemical transformation, and the preparation method has the characteristics of complex process and poor reproducibility. Therefore, a simple method is searched for shortening the preparation process flow, reducing the production cost, always keeping the unique micro-nano structure and the enhanced electrochemical performance, and the method has very important significance in the technical fields of nano material preparation and new energy.
Disclosure of Invention
Aiming at the process complexity of the prior art, the invention provides a simple method for preparing a nickel-cobalt-zinc trimetal hydroxide/oxyhydroxide composite material by one step through solvothermal reaction and application thereof, phase control of the nickel-cobalt-zinc trimetal hydroxide/oxyhydroxide composite material can be effectively realized by changing the solvothermal time, the composite phase material is prepared by one step, the preparation process of the material is accelerated, the production cost is reduced, a stable micro-nano structure is always kept, the method has the characteristics of simple process, good reproducibility and the like, and the method has excellent comprehensive performance when being used as the positive electrode of a super capacitor.
The invention is realized by the following technical scheme:
a method for preparing a nickel-cobalt-zinc hydroxide/oxyhydroxide composite material by using a one-step method. The method comprises the following steps:
(a) Respectively dissolving cobalt salt and 2-methylimidazole in methanol, fully stirring and dissolving to form a solution, quickly pouring the 2-methylimidazole solution into the cobalt salt solution, fully stirring, standing, ageing, filtering, collecting, and vacuum-drying to obtain a ZIF-67 template material of a metal organic framework material;
wherein the cobalt salt is cobalt nitrate hexahydrate; the concentration is 100 mmol/L; the concentration of the 2-methylimidazole is 400 mmol/L; stirring the mixed solution for 30-60 min; the aging time is 24 h; filtering with ethanol solution; the vacuum drying temperature is 50-100 ℃, and the drying time is 10-24 h;
(b) Ultrasonically dispersing a ZIF-67 template in a solvent to obtain a mixed system A, sequentially dissolving nickel salt and zinc salt in the solvent to obtain a solution B, pouring the solution B into the mixed system A, fully stirring, and transferring to an oven for solvothermal reaction. Cooling to room temperature, washing to remove impurities in the product, and drying the obtained product in vacuum to obtain the nickel-cobalt-zinc trimetal hydroxide/oxyhydroxide composite material;
(c) Preparing the positive electrode of the super capacitor: the obtained nickel-cobalt-zinc trimetal hydroxide/oxyhydroxide composite material, a conductive agent and a binder are prepared into slurry according to a certain proportion and are uniformly coated on foamed nickel, the slurry is dried in vacuum at the temperature of 110 ℃, and finally the slurry is pressed into a working electrode under the pressure of 10 MPa.
Preferably, in the step B, the solvent of the mixed system A is methanol, and the solvent of the solution B is ethanol.
Preferably, the volume ratio of methanol to ethanol in step b is 1.
Preferably, the nickel salt and the zinc salt in step b are nickel nitrate hexahydrate and zinc nitrate hexahydrate, respectively.
Preferably, the nickel salt and the zinc salt are used in the step b at concentrations of 28 mmol/L and 5.4 mmol/L respectively.
Preferably, the mass ratio of the ZIF-67 to the nickel salt in the step b is 1.
Preferably, the solvothermal reaction temperature in step b is 120 ℃.
Preferably, the solvothermal reaction temperature in the step b is 0.5 h,2 h,4 h and 8 h.
Further, deionized water and ethanol are used for washing and impurity removal in the step b.
Further, the product obtained in the step b is dried in vacuum at 50-100 ℃ for 10-24 h.
Further, the obtained nickel-cobalt-zinc trimetal hydroxide/oxyhydroxide composite material is green powder.
A nickel cobalt zinc trimetal hydroxide/oxyhydroxide composite obtained by the one-step method for preparing a nickel cobalt zinc hydroxide/oxyhydroxide composite as described in any one of the preceding claims.
Compared with the prior art, the invention has the beneficial effects that:
the invention has the advantages that 1, the simple nickel-cobalt-zinc trimetal hydroxide/oxyhydroxide composite material and the preparation method thereof are provided, phase control of the nickel-cobalt-zinc trimetal material can be effectively realized by changing the hot time of the solvent, the composite phase material of the hydroxide and the oxyhydroxide is prepared in one step, the complex process that the pure phase material is prepared firstly and then the pure phase material is deposited through a chemical bath or is converted through electrochemistry under the traditional process is avoided, the material preparation process is accelerated, and the production cost is reduced;
and 2, the composite phase material always keeps a stable micro-nano structure, has the characteristics of stable process and good reproducibility, and also shows excellent specific capacity, rate capability and cycling stability when used as the positive electrode of the super capacitor.
Drawings
FIG. 1 is an X-ray diffraction (XRD) contrast pattern of the Ni-Co-Zn trimetallic materials obtained in examples 1-4.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the Ni-Co-Zn trimetal hydroxide/oxyhydroxide obtained in example 1.
FIG. 3 is a Scanning Electron Microscope (SEM) image of the Ni-Co-Zn trimetal hydroxide/oxyhydroxide obtained in example 2.
FIG. 4 is a Scanning Electron Microscope (SEM) image of the Ni-Co-Zn trimetal hydroxide/oxyhydroxide obtained in example 3.
Fig. 5 is a Scanning Electron Microscope (SEM) image of the nickel cobalt zinc trimetal hydroxide obtained in example 4.
Fig. 6 is a Transmission Electron Microscope (TEM) image of the nickel cobalt zinc trimetal hydroxide/oxyhydroxide composite obtained in example 1.
FIG. 7 is a comparison graph of Cyclic Voltammetry (CV) at a scan rate of 5 mV/s for the Ni-Co-Zn trimetallic materials obtained in examples 1-4.
FIG. 8 is a comparative image of constant current charge and discharge (GCD) at a current density of 1A/g for the Ni-Co-Zn trimetallic materials obtained in examples 1-4.
FIG. 9 is a graph showing the comparison of the magnification performance of the Ni-Co-Zn trimetal materials obtained in examples 1-4 at different scanning speeds.
FIG. 10 is a graph of the lifetime of the nickel cobalt zinc trimetal hydroxide/oxyhydroxide obtained in example 1 at a current density of 30A/g.
Detailed Description
The technical solution of the present invention will now be described in detail by the following specific examples.
Example 1
Step 1, respectively dissolving 1.45 g of cobalt nitrate hexahydrate and 1.64 g of 2-methylimidazole in 50 mL of methanol, fully stirring and dissolving to form a solution, quickly pouring the 2-methylimidazole solution into the cobalt nitrate solution, fully stirring for 30 min, standing and aging for 24 h, performing suction filtration and washing by using ethanol, collecting a sample, and performing vacuum drying at 80 ℃ for 12 h to obtain a metal organic framework material ZIF-67 material;
and 2, ultrasonically dispersing 50 mg of ZIF-67 in 25 mL of methanol to obtain a mixed system A, sequentially dissolving 200 mg of nickel nitrate hexahydrate and 40 mg of nickel zinc nitrate hexahydrate in 5 mL of ethanol to obtain a solution B, pouring the solution B into the mixed system A, fully stirring for 1 h, transferring into an oven, carrying out solvothermal reaction at 120 ℃ for heat preservation for 2.0 h, cooling to room temperature, washing with deionized water and ethanol to remove impurities in a product, and carrying out vacuum drying on the obtained product at 80 ℃ to obtain the nickel-cobalt-zinc trimetal hydroxide/oxyhydroxide composite material.
Example 2
The method of the present embodiment is substantially the same as embodiment 1, except that: and (3) adjusting the solvothermal reaction time length in the step (2) to 0.5 h to obtain the nickel-cobalt-zinc trimetal hydroxide/oxyhydroxide composite material.
Example 3
The method of the present embodiment is substantially the same as embodiment 1, except that: and (3) adjusting the solvothermal reaction time length in the step (2) to 4 h to obtain the nickel-cobalt-zinc trimetal hydroxide/oxyhydroxide composite material.
Example 4
The method of the present embodiment is substantially the same as embodiment 1, except that: and (3) adjusting the solvothermal reaction time length in the step (2) to 8 h to obtain the pure-phase nickel-cobalt-zinc trimetal hydroxide material.
Application example 1
Mixing the prepared sample, acetylene black as a conductive agent and a binder (polyvinylidene fluoride and PVDF) according to the mass ratio of 7. A three-electrode system is used, a coated electrode slice is used as a working electrode, a platinum slice electrode is used as a counter electrode, a mercury oxide electrode is used as a reference electrode, a cyclic voltammetry curve test and a constant current charge-discharge performance test are carried out in 2M KOH electrolyte by using CHI660E, and a cyclic stability test is carried out by using LAND CT 2001A.
As can be seen from fig. 4, the cyclic voltammograms all have a pair of distinct redox peaks, which indicates that the nickel-cobalt-zinc trimetal material prepared by the present invention has a significant faraday cell reaction characteristic, while at the same sweep rate, the cyclic voltammogram area of the sample in example 1 is the largest, which indicates that the nickel-cobalt-zinc trimetal hydroxide/oxyhydroxide composite material obtained after 2 h of heat preservation has the optimal electrochemical performance. As can be seen from fig. 5, the constant current charging and discharging test has a pair of distinct charging and discharging plateaus, and the sample of example 1 has the longest discharging time, i.e. the highest capacity value, under the same current density. As can be seen from FIG. 6, the capacity value of the nickel cobalt zinc trimetal hydroxide/oxyhydroxide composite material prepared in example 1 can reach 2069F/g at a current density of 1A/g, and when the current density is increased by 100A/g, the capacity retention rate is 63.5%, which proves that the nickel cobalt zinc trimetal hydroxide/oxyhydroxide composite material has excellent rate capability. As can be seen from FIG. 7, the nickel-cobalt-zinc trimetal hydroxide/oxyhydroxide composite material prepared in the invention in the embodiment 1 has no attenuation after 37000 cycles at a current density of 30A/g, and has excellent cycling stability.
Claims (8)
1. A method for preparing a nickel-cobalt-zinc hydroxide/oxyhydroxide composite material by using a one-step method is characterized by comprising the following steps of:
(a) Preparing a ZIF-67 template: respectively dissolving cobalt salt and 2-methylimidazole in methanol, fully stirring and dissolving to form a solution, quickly pouring the 2-methylimidazole solution into the cobalt salt solution, fully stirring, standing, ageing, filtering, collecting, and vacuum-drying to obtain a ZIF-67 template of the metal organic framework material;
(b) Preparing a nickel-cobalt-zinc hydroxide/oxyhydroxide composite material: ultrasonically dispersing a ZIF-67 template in a solvent to obtain a mixed system A, sequentially dissolving nickel salt and zinc salt in the solvent to obtain a solution B, pouring the solution B into the mixed system A, fully stirring, transferring into a drying oven for solvent thermal reaction, cooling to room temperature, washing to remove impurities in a product, and performing vacuum drying on the obtained product to obtain a nickel-cobalt-zinc trimetal hydroxide/oxyhydroxide composite material;
(c) Preparing the positive electrode of the super capacitor: preparing the obtained nickel-cobalt-zinc trimetal hydroxide/oxyhydroxide composite material, a conductive agent and a binder into slurry according to a certain proportion, uniformly coating the slurry on foamed nickel, drying the foamed nickel in vacuum at 110 ℃, and finally pressing the foamed nickel into a working electrode under the pressure of 10 MPa;
in step a, the cobalt salt is cobalt nitrate hexahydrate; the concentration is 100 mmol/L; the concentration of the 2-methylimidazole is 400 mmol/L; stirring the mixed solution for 30 min; the aging time is 24 h; filtering with ethanol solution; the vacuum drying temperature is 80 ℃, and the drying time is 12 h.
2. The preparation method according to claim 1, wherein the mixed solvent A in the step B is methanol, and the solvent B in the solution B is ethanol, and the volume ratio of the two is 1.
3. The method according to claim 1, wherein the nickel salt and the zinc salt in step b are nickel nitrate hexahydrate and zinc nitrate hexahydrate in concentrations of 28 mmol/L and 5.4 mmol/L, respectively.
4. The preparation method according to claim 1, wherein the mass ratio of the ZIF-67 to the nickel salt in the step b is 1.
5. The method of claim 1, wherein the solvothermal reaction temperature in step b is 120 ℃.
6. The preparation method of claim 1, wherein the solvothermal reaction time in the step b is 0.5 to 8 hours.
7. The nickel-cobalt-zinc hydroxide/oxyhydroxide composite material obtained by the preparation method according to any one of claims 1 to 6 is characterized by having a uniform hollow rhombic dodecahedron structure and obvious thin-layer nanosheets, having a high specific surface area, being simple in process, requiring no subsequent complex transformation process and having good reproducibility.
8. The one-step method for preparing the nickel-cobalt-zinc hydroxide/oxyhydroxide composite material according to claim 7, wherein the material can be used as a positive electrode material of a super capacitor, and has excellent capacity, rate capability and ultra-long cycle stability due to the unique two-phase structure and good conductivity generated in situ.
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| CN202210896126.6A CN115206686A (en) | 2022-07-28 | 2022-07-28 | Method for preparing nickel-cobalt-zinc hydroxide/oxyhydroxide composite material by one-step method |
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