CN111921529A - Preparation method and application of nickel-cobalt metal organic framework/nickel-cobalt metal hydroxide heterogeneous material - Google Patents
Preparation method and application of nickel-cobalt metal organic framework/nickel-cobalt metal hydroxide heterogeneous material Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 33
- -1 nickel-cobalt metal hydroxide Chemical class 0.000 title claims abstract description 19
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000002057 nanoflower Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 239000002135 nanosheet Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 11
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 229910017709 Ni Co Inorganic materials 0.000 claims 4
- 229910003267 Ni-Co Inorganic materials 0.000 claims 4
- 229910003262 Ni‐Co Inorganic materials 0.000 claims 4
- 150000004692 metal hydroxides Chemical class 0.000 claims 3
- 239000003990 capacitor Substances 0.000 abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 abstract description 8
- 150000003624 transition metals Chemical class 0.000 abstract description 8
- 239000013110 organic ligand Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000005342 ion exchange Methods 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 abstract 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 abstract 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 29
- 238000004146 energy storage Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229910015386 Ni0.9Co0.1(OH)2 Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001808 coupling effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- 229910016719 Ni0.5Co0.5(OH)2 Inorganic materials 0.000 description 1
- 229910017270 Ni0.8Co0.2(OH)2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
The invention belongs to a preparation method and application of a Metal Organic Framework (MOF) and transition metal hydroxide heterogeneous material, and discloses a three-dimensional nanoflower composite material consisting of a nickel-cobalt metal organic framework/nickel-cobalt metal hydroxide two-dimensional heterogeneous nanosheet and application of the three-dimensional nanoflower composite material in the aspect of super-capacitor performance, wherein the nickel-cobalt metal hydroxide is used as a precursor and a template, and an organic ligand is obtained in a partial ion exchange mode. The invention adopts a two-step synthesis technology, and firstly urea, cobalt nitrate and nickel nitrate are utilized to self-assemble in a system taking distilled water as a solvent to obtain NiCo (OH) with a nanoflower structure2(ii) a Then, the organic ligand of the terephthalic acid and NiCo (OH) are utilized2Obtaining ultrathin NiCo-MOF/NiCo (OH) with uniform distribution size and size in a mixed solution of N, N-dimethylformamide, ethanol and water in a partial ion exchange mode2The nanometer flower structure. In addition, the invention has a large number of active sites, good reactivity and conductivity, so that the super-capacitor has good super-capacitor performance.
Description
Technical Field
The invention belongs to the field of nano material preparation technology and energy storage, and particularly relates to a novel metal organic framework and transition metal hydroxide composite material and an energy storage application thereof in the field of super capacitors.
Background
The ever-increasing demand for clean, renewable energy and energy supplies and mobile power sources has faced a number of technical challenges while increasing the demand for efficient and safe energy conversion and storage devices. As one energy storage device, the super capacitor is a novel energy storage device between an electrolytic capacitor and a battery, and has the advantages of long cycle life, large-current charging and discharging, high discharging power, super-large capacity at the Faraday level, no maintenance, economy, environmental protection and the like, so the super capacitor has wide application prospect in the fields of hybrid electric vehicles, military devices, high-power electric devices, portable electronic devices and the like. And the electrode material is the most important factor influencing the performance of the super capacitor.
In recent years, metal organic framework materials have become one of the hot research directions of coordination chemistry and material science due to the diversity of the structure, the unique functional characteristics and the potential application prospects in multiple fields. The material is widely considered as a potential electrode material of a super capacitor, but the material still has the defects of low conductivity and reactivity.
Disclosure of Invention
Based on the above, the metal organic framework and transition metal hydroxide composite material provided by the invention is an MOF-based composite material with high specific surface area, high ion transmission efficiency and reaction activity obtained by using transition metal hydroxide as a precursor and an organic ligand in a partial ion exchange mode and controlling the raw material ratio of the transition metal hydroxide and the organic ligand, and is used for the performance research of a supercapacitor.
The technical scheme of the invention is as follows: a nickel-cobalt metal organic framework/nickel-cobalt metal hydroxide heterogeneous material with a multilevel structure is formed by mixing nickel and cobalt, wherein the average diameter of the nanoflower material is 1-5 mu m, and the thickness of petals is about 1-10 nm.
A method of making the material, the method comprising the steps of:
1) dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate and urea in water, and performing ultrasonic dispersion and uniform mixing at room temperature;
2) transferring the mixed solution obtained in the step 1) into a polytetrafluoroethylene lining, and filling the polytetrafluoroethylene lining with the mixed solution
Carrying out hydrothermal reaction in a steel container at 140-180 ℃ for 3-12 h (preferably 160 ℃ for 2 h), and cooling for 8h to room temperature.
3) Centrifuging the sample obtained in the step 2), collecting precipitates, respectively centrifuging and washing the precipitates with ethanol and water for multiple times, and drying the obtained product in vacuum to obtain NiCo (OH) with a nanoflower structure2。
The molar ratio of the cobalt nitrate hexahydrate, the nickel nitrate hexahydrate and the urea in the step (1) is 0.05-1:0.05-1: 1-8. The molar ratio of the cobalt nitrate hexahydrate to the nickel nitrate hexahydrate to the urea is 0.1-1:0.1-0.9:6, and NiCo (OH) with a nanometer flower structure is prepared2. Preferably 0.1:0.9:1-6, 0.2:0.8:1-6, 0.3:0.7:1-6, 0.4:0.6:1-6, 0.5:0.5:1-6, 0.6:0.4:1-6, 0.7:0.3:1-6. Further optimized to be 0.1:0.9:1-6, and finally, the molar ratio of the cobalt nitrate hexahydrate to the nickel nitrate hexahydrate to the urea is preferably 0.1:0.9: 6.
The centrifugation speed of each step (3) is 6000rpm @ min, and the centrifugation time is 5 min. The vacuum drying temperature is 80 ℃, the pressure is 10MPa, and the time is 12-16 hours.
4) The NiCo (OH) is obtained in the step 3)2Dissolving the mixture with terephthalic acid in a mixed solution of N, N-dimethylformamide, deionized water and ethanol, and performing ultrasonic treatment at room temperature to uniformly mix reactants.
5) Transferring the mixed solution obtained in the step 4) into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into a stainless steel container for hydrothermal reaction at the temperature of 120-160 ℃ for 24-72h (preferably at the temperature of 140 ℃ for 48 h), and cooling for 8h to room temperature.
6) Centrifuging the sample obtained in the step 5), collecting precipitate, separately and centrifugally washing the precipitate for multiple times by using N, N-dimethylformamide and water, and carrying out vacuum drying on the obtained product to obtain NiCo-MOF/NiCo (OH) consisting of two-dimensional nano sheets with the thickness of about 5 nm2Three-dimensional nanometer flower composite material.
Said step 4) NiCo (OH)2And the molar mass ratio of the terephthalic acid is 1: 0.1-10. Preferably 0.5:1-10, 1: 1-10. Further optimized to be 1: 1-10. NiCo (OH)2When the molar ratio of the terephthalic acid is 1:0.1-2, preparing NiCo-MOF @ NiCo (OH) with a nano flower-shaped multi-stage structure consisting of ultrathin two-dimensional nano sheets2A composite material. NiCo (OH)2And the molar ratio of terephthalic acid to terephthalic acid is 1:4-10, and the NiCo-MOFs metal organic framework material consisting of the two-dimensional nano sheets is prepared. Final preference is NiCo (OH)2The molar ratio of terephthalic acid was 1: 1.
The volume ratio of the N, N-dimethylformamide to the water to the ethanol in the mixed solution in the step (4) is 14-32:0.1-2: 0.1-2. Preferably, the volume ratio of the N, N-dimethylformamide to the water to the ethanol in the mixed solution is 16:1: 1.
The centrifugation speed of each time in the step (6) is 8000rpm/min, and the centrifugation time is 6 min. The vacuum drying temperature is 80 ℃, the pressure is 10MPa, and the time is 12-16 hours.
A similar approach can be used to prepare individual NiCo-MOF nanosheet metal organic framework materials, NiCo (OH) in step (4)2And the molar ratio of the terephthalic acid is 1: 4-10.
The other technical scheme of the invention is to apply the nickel-cobalt metal organic framework/nickel-cobalt metal hydroxide heterogeneous material to the super capacitor.
The invention has the following beneficial effects:
(1) the material has simple synthesis method, the price of the preparation raw materials is low, the raw materials are easy to obtain, and the nano flower with relatively stable nano size can be formed by controlling the reaction time and the reaction temperature.
(2) The synthesis of the nano flower material effectively improves the specific surface area of the material and is more beneficial to the transmission of ions.
(3) Due to the advantages of structure and composition, the material has good super-capacitor performance, specific capacitance can reach 3100F/g when current density is 1A/g, and good rate performance and cycle stability are achieved.
(4) The material better plays the coupling effect between the MOF and the inorganic material, ensures rich oxidation-reduction reaction and good conductivity, and leads the three-dimensional nano flower metal organic framework material NiCo-MOF/NiCo (OH)2The performance of the super capacitor is better than that of NiCo (OH)2And NiCo-MOF.
(5) The method has the advantages of simple process, easy operation and low requirement on equipment, and the prepared electrode is firmly combined with the substrate, has excellent specific capacitance and stability, and can be widely applied to the field of super-capacitor energy storage.
(6) The invention provides a new idea for designing and synthesizing a reasonably adjustable MOF structure so as to improve the electrochemical properties of energy storage and conversion.
Drawings
FIG. 1 shows Ni synthesized in example 10.9Co0.1(OH)2EXAMPLE 4 NiCo-MOF/Ni Synthesis0.9Co0.1(OH)2-X-ray diffraction patterns of the sample 1 and of the NiCo-MOF sample synthesized in example 7.
FIG. 2 shows Ni synthesized in example 10.9Co0.1(OH)2EXAMPLE 4 NiCo-MOF/Ni Synthesis0.9Co0.1(OH)2-infrared absorption spectra of sample 1 and NiCo-MOF sample synthesized in example 7.
FIG. 3 shows Ni synthesized in example 10.9Co0.1(OH)2Scanning electron micrographs of the samples.
FIG. 4 is NiCo-MOF/Ni synthesized in example 40.9Co0.1(OH)2-1 scanning electron micrograph of sample.
FIG. 5 is a scanning electron micrograph of a sample of NiCo-MOF synthesized in example 7.
FIG. 6 shows NiCo-MOF/Ni synthesized in example 40.9Co0.1(OH)2CV curves of the samples at different sweep rates.
FIG. 7 is NiCo-MOF/Ni synthesized in example 40.9Co0.1(OH)2-1 charge and discharge curves of the sample at different current densities.
FIG. 8 shows Ni synthesized in example 10.9Co0.1(OH)2EXAMPLE 4 NiCo-MOF/Ni Synthesis0.9Co0.1(OH)2-1 sample and NiCo-MOF sample synthesized in example 7 at a current density of 0.5A/g.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the invention as claimed is not limited to the scope of the examples.
Example 1 (Ni)0.9Co0.1(OH)2Preparation of (1)
Dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate and urea in a mixed solution prepared from 30mL of deionized water according to a molar ratio of 0.1:0.9:6, and performing ultrasonic treatment at room temperature for 20min to uniformly mix reactants to obtain a mixed solution A. Transferring the mixed solution A into a 50mL polytetrafluoroethylene lining, putting the mixed solution A into a stainless steel container, preserving the heat for 2 hours at the temperature of 160 ℃, and cooling for 8 hours to room temperature to obtain grayish blue solid powder. Centrifuging and washing ethanol and water for three times respectively at the rotating speed of 6000rpm @ min for 5min @ times, vacuum drying the obtained product at the temperature of 80 ℃ for 12-16 hours to obtain a material with a nanoflower structure, wherein the obtained sample is high-purity Ni0.9Co0.1(OH)2。
Example 2 (Ni)0.8Co0.2(OH)2Preparation of (1)
High-purity Ni can be obtained by changing the molar ratio of cobalt nitrate hexahydrate to nickel nitrate hexahydrate to urea in the ratio of 0.2:0.8:6 and other experimental conditions as in example 10.8Co0.2(OH)2
Example 3 (Ni)0.5Co0.5(OH)2Preparation of (1)
High-purity Ni can be obtained by changing the molar ratio of cobalt nitrate hexahydrate to nickel nitrate hexahydrate to urea in the ratio of 0.5:0.5:6 and other experimental conditions as in example 10.5Co0.5(OH)2。
Example 4 (NiCo-MOF/Ni)0.9Co0.1(OH)2Preparation of (1)
Mixing Ni in a molar ratio of 1:0.50.9Co0.1(OH)2Dissolving terephthalic acid in a mixed solution prepared from N, N-dimethylformamide at a ratio of 15:1:1, ethanol and deionized water, and performing ultrasonic treatment at room temperature for 20min to uniformly mix reactants to obtain a mixed solution. And then transferring the mixed solution into a 50mL polytetrafluoroethylene lining, putting the lining into a stainless steel container, preserving the temperature for 48 hours at the temperature of 140 ℃, and cooling the lining for 8 hours to room temperature to obtain solid powder crystals. Respectively and centrifugally washing with N, N-dimethylformamide and water for three times at the rotating speed of 8000rpm @ min and the centrifugal time of 6min @ times, and drying the obtained product in vacuum at the temperature of 80 ℃ for 12-16 hours to obtain NiCo-MOF/NiCo (OH) consisting of two-dimensional nano sheets with the thickness of about 1-10 nm2The three-dimensional nanoflower composite material is obtained, and the obtained sample is high-purity NiCo-MOF/Ni0.9Co0.1(OH)2-1 nanoflower.
Example 5 (NiCo-MOF/Ni)0.9Co0.1(OH)2Preparation of NiCo-2)
Changing the above Ni0.9Co0.1(OH)2And terephthalic acid in a ratio of 1:1, under otherwise identical experimental conditions as in example 4, NiCo-MOF/Ni of high purity was obtained0.9Co0.1(OH)2NiCo-2 nanoflower.
Example 6 (NiCo-MOF/Ni)0.9Co0.1(OH)2Preparation of (E) -3)
Changing the above Ni0.9Co0.1(OH)2And terephthalic acid in a ratio of 1:2, under otherwise identical experimental conditions as in example 4, NiCo-MOF/Ni of high purity was obtained0.9Co0.1(OH)2-3 nanoflower.
Example 7 (preparation of NiCo-MOF)
Changing the above Ni0.9Co0.1(OH)2And terephthalic acid in a ratio of 1:5, and obtaining NiCo-MOF nanosheets with high purity under the same other experimental conditions as in example 4.
Example 8
After the metal organic framework and the transition metal hydroxide composite material are basically characterized, the super-capacitor performance test is carried out on the metal organic framework and the transition metal hydroxide composite material, and the specific method is as follows:
weighing 4mg of the samples in the 7 embodiments, adding 0.2 ml of naphthol, 1.3 ml of deionized water and 0.5 ml of ethanol, and carrying out ultrasonic mixing for 30min to prepare an electrode solution for later use; and coating 2-10 microliters of the electrode solution on a glass electrode to form a working electrode, taking a platinum wire as a counter electrode, and taking a saturated calomel electrode as a reference electrode to perform a super-capacitive performance test in a 1M KOH solution. Obtaining Ni at a current density of 1A/g0.9Co0.1(OH)2 (1640 F/g)>Ni0.8Co0.2(OH)2(1485 F/g)>Ni0.5Co0.5(OH)2(1140F/g) and thus the optimum precursor and templating agent (Ni) are selected0.9Co0.1(OH)2) NiCo-MOF/Ni prepared0.9Co0.1(OH)2-1(3100F/g)>NiCo-MOF/Ni0.9Co0.1(OH)2NiCo-2(2400F/g)>NiCo-MOF/Ni0.9Co0.1(OH)2-3(1700F/g)>NiCo-MOF (1400F/g) has higher composite capacitance than pure NiCo (OH) at a current density of 1A/g2And NiCo-MOF, and example 5 NiCo-MOF/Ni0.9Co0.1(OH)2-1 has good rate and cycle performance.
NiCo-MOF @ Ni prepared as described in example 5 above0.9Co0.1(OH)2-2, the performance test of the sample is shown in fig. 6-7, the super capacitor constructed by the material belongs to a pseudo capacitor and generates an oxidation-reduction reaction, fig. 8, the constant current charge and discharge test under the same current density is respectively carried out on the material before and after compounding, and the result shows that the coupling effect between metals is good, and the performance of the super capacitor is well improved.
Researches show that the electrochemical performance of the material can be optimized by adjusting the structure and the composition of the material, in the technical scheme of the invention, transition metal hydroxide is used as a precursor and a template, and an organic ligand obtains NiCo-MOF/NiCo (OH) composed of two-dimensional nano sheets with the thickness of about 1-10 nm in a partial ion exchange mode2Three-dimensional nano-flower composite material, which benefits from structural and compositional advantages and the coupling effect between metals, prepared NiCo-MOF/NiCo (OH)2The nanoflower electrode has excellent super-capacitance performance, better rate performance and longer cycle life. This work provides a new concept for designing and synthesizing reasonably tunable MOF structures to improve the electrochemical performance of energy storage and switching.
The above-described embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and features in the embodiments and examples in the present application may be arbitrarily combined with each other without conflict. The protection scope of the present invention is defined by the claims, and includes equivalents of technical features of the claims. I.e., equivalent alterations and modifications within the scope hereof, are also intended to be within the scope of the invention.
Claims (10)
1. A preparation method of a nickel-cobalt metal organic framework/nickel-cobalt metal hydroxide heterogeneous material is characterized by comprising the following steps:
(1) dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate and urea in water, and performing ultrasonic dispersion and uniform mixing at room temperature;
(2) transferring the mixed solution obtained in the step (1) to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and cooling to room temperature after hydrothermal reaction;
(3) centrifuging the sample obtained in the step (2), collecting precipitate, respectively centrifuging and washing with ethanol and water, and vacuum drying to obtain NiCo (OH) with a nanoflower structure2；
(4) Dissolving the sample obtained in the step (3) and terephthalic acid in a mixed solution of N, N-dimethylformamide, water and ethanol, and performing ultrasonic dispersion and uniform mixing at room temperature;
(5) transferring the mixed solution obtained in the step (4) to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and cooling to room temperature after hydrothermal reaction;
(6) centrifuging the sample obtained in the step (5) to collect precipitate, respectively centrifuging and washing with N, N-dimethylformamide and ethanol, and then drying in vacuum to obtain NiCo-MOF/NiCo (OH) consisting of two-dimensional nano-sheets2Three-dimensional nanometer flower composite material, namely nickel cobalt metal organic framework/nickel cobalt metal hydroxide heterogeneous material.
2. The method of claim 1, wherein the molar ratio of cobalt nitrate hexahydrate, nickel nitrate hexahydrate, and urea in step (1) is 0.05-1:0.05-1: 1-8.
3. The method for preparing a nickel cobalt metal organic framework/nickel cobalt metal hydroxide heterogeneous material according to claim 2, wherein the molar ratio of cobalt nitrate hexahydrate, nickel nitrate hexahydrate and urea in step (1) is 0.1-1:0.1-0.9:6, so that NiCo (OH) with a nanoflower structure is prepared2。
4. The nickel cobalt metal organic framework/nickel cobalt metal hydroxide heterogeneous material of claim 3, wherein step (4) NiCo (OH)2The molar ratio of terephthalic acid is 1: 0.1-10.
5. The method of claim 4, wherein the step (4) NiCo (OH)2When the molar ratio of the terephthalic acid is 1:0.1-2, preparing NiCo-MOF @ NiCo (OH) with a nano flower-shaped multi-stage structure consisting of ultrathin two-dimensional nano sheets2A composite material.
6. The nickel cobalt metal organic framework/nickel cobalt of claim 4The preparation method of the metal hydroxide heterogeneous material is characterized in that the step (4) NiCo (OH)2And the molar ratio of terephthalic acid to terephthalic acid is 1:4-10, and the NiCo-MOFs metal organic framework material consisting of the two-dimensional nano sheets is prepared.
7. The method of claim 1 wherein the volume ratio of N, N-dimethylformamide, water and ethanol in the mixed solution is 14-32:0.1-2: 0.1-2.
8. The method for preparing Ni-Co metal organic skeleton/Ni-Co metal hydroxide heterogeneous material according to claim 1, wherein the hydrothermal reaction temperature in step (2) is 140-180 ℃ and the reaction time is 3-12 h.
9. The method for preparing Ni-Co metal organic skeleton/Ni-Co metal hydroxide heterogeneous material according to claim 1, wherein the hydrothermal reaction temperature in step (5) is 120-160 ℃, and the reaction time is 24-72 h.
10. Use of the nickel cobalt metal organic framework/nickel cobalt metal hydroxide heterogeneous material prepared by the method according to any one of claims 1 to 9 in a supercapacitor.
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