CN115725084A - Flaky nickel-cobalt bimetal organic framework crystal material and preparation method thereof - Google Patents
Flaky nickel-cobalt bimetal organic framework crystal material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flaky nickel-cobalt bimetal organic framework crystal material and a preparation method thereof. Dissolving soluble salts of nickel and cobalt, terephthalic acid and polyvinylpyrrolidone into a dimethyl imidazole solution, soaking activated carbon cloth into the mixed solution after uniform dissolution, and carrying out hydrothermal reaction in a closed reaction kettle; after hydrothermal reaction, naturally cooling to normal temperature, washing and drying to obtain the flaky nickel-cobalt bimetal organic framework crystal loaded on the surface of the activated carbon cloth. The method has the advantages of simple process, convenient operation and low cost, the obtained flaky crystals are uniformly distributed, the specific surface area of the crystal particles is increased by the flaky structure, the contact area with the electrolyte can be enlarged by increasing the specific surface area, the transmission of electrolyte ions is accelerated, and the method has wide application prospect in the field of novel energy materials.
Description
Technical Field
The invention belongs to the technical field of preparation of electrode materials of super capacitors, and particularly relates to a flaky nickel-cobalt bimetal organic framework crystal material and a preparation method thereof.
Background
Metal Organic Framework (MOF) Materials have attracted extensive attention in the field of supercapacitor electrode Materials [ Wang Y, et al. ACS Applied Energy Materials,2019,2 (3) ] because of their high surface area, abundant active sites, diverse structures and easy regulation. Researches show that the metal organic framework material with the sheet structure can increase the specific surface area of the material, enlarge the contact area with the electrolyte and accelerate the transmission of electrolyte ions. The synergistic effect of the double metal ions has stronger electron storage capacity [ Chen C, et al.2018,47,5639-5645] compared with single metal, and shows more excellent electrochemical performance.
The existing synthesis path of the metal organic framework material is commonly a hydrothermal method or a solvothermal method, and the obtained metal organic framework material has uniform morphological characteristics due to the characteristics of hydrothermal reaction at high temperature and high pressure. Gao and the like adopt a hydrothermal method to synthesize NiCo-MOF in a dandelion shape, and cobalt ions partially replace nickel ions in a Ni-MOF structure, so that the crystallinity is reduced, and the structure of MOFs is changed from a waxberry shape to a dandelion shape. Lower crystallinity enhances conductivity, and nanorods dispersed on the surface of dandelion-like spheres facilitate ion transport, which all enhance the capacitive properties [ Gao S, et al. Journal of Colloid and Interface Science,2018, 531. Zhang et al synthesized a sheet-like Ni-Co bimetallic organic framework, and the prepared sheet-like NiCo-MOF electrode had high specific capacitance, good rate capability and long-term cycle stability [ Zhang X, et al. Journal of Materials Science: materials in Electronics,2020,27 (4) ]; the Habib Gholipour-Ranjbar and the like have the effects of both a solvent and a ligand by using a pyrazine solution, a nickel-cobalt-based bimetallic organic framework is synthesized by a hydrothermal method, and the prepared bimetallic organic framework has good rate performance and cycle retention rate. NiCo-MOF has lower charge transfer resistance and ion diffusion barrier compared to Ni-MOF [ Gholipoour-Ranjbar H et al.New Journal of Chemistry,2016 10.1039.C6NJ01449F ].
At present, most of the research is carried out on the nickel-cobalt bimetallic organic framework prepared by a single ligand, and there are few reports about the nickel-cobalt bimetallic organic framework combined by double ligands. Most of the prepared bimetallic organic frame material and composite material thereof are in a powder state, and when the bimetallic organic frame material and the composite material thereof are applied, a binder is required to prepare an electrode material, so that the conductivity of an electrode system is greatly reduced.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a flaky nickel-cobalt bimetal organic framework crystal material and a preparation method thereof. According to the preparation method, bi-directional synergistic effects among bimetallic nickel ions and cobalt ions and with a dual ligand are fully utilized, a nickel-cobalt bimetallic organic framework crystal with a sheet structure can be directly grown on the surface of the activated carbon cloth through the high-temperature and high-pressure effects of a hydrothermal reaction and the regulation and control of various reaction parameters, and the obtained composite material with the sheet structure has low density, high specific surface area and good conductivity and has good advantages in the application of electrode materials of super capacitors.
The technical scheme adopted by the invention is as follows:
1. flaky nickel-cobalt bimetal organic framework crystal material
Dimethyl imidazole and terephthalic acid are used as mixed organic ligands, nickel nitrate hexahydrate and cobalt nitrate hexahydrate are used as reactants, and a flaky nickel-cobalt bimetal organic framework crystal loaded on the surface of active carbon cloth is obtained through a hydrothermal reaction; the nickel-cobalt bimetallic organic framework crystals exhibit a uniform lamellar structure with an average thickness of 0.15 to 0.20. Mu.m.
2. Preparation method of flaky nickel-cobalt bimetal organic framework crystal material
The method comprises the following steps:
1) Dissolving nickel nitrate hexahydrate and cobalt nitrate hexahydrate in a dimethyl imidazole solvent, and uniformly stirring to obtain a mixed solution A;
2) Adding terephthalic acid and polyvinylpyrrolidone into the mixed solution A, and continuously stirring to obtain a mixed solution B; the dosage of the polyvinylpyrrolidone is 1.5g;
3) Soaking the treated activated carbon cloth in the mixed solution B for ultrasonic treatment for 1 hour;
4) Carrying out hydrothermal reaction on the solution obtained in the step 3) and the activated carbon cloth in a 100mL reaction kettle;
5) Naturally cooling the reaction kettle after the reaction in the step 4) to normal temperature, repeatedly cleaning the reaction kettle with absolute ethyl alcohol and deionized water for three times, and drying to obtain the flaky nickel-cobalt bimetallic organic framework crystal uniformly grown on the surface of the activated carbon cloth.
In the step 1):
the molar mass ratio of nickel nitrate hexahydrate to cobalt nitrate hexahydrate is 1;
the molar concentration of the dimethyl imidazole solvent is 0.2mol/L, and the dosage is 30mL.
The total molar concentration of the nickel ions and the cobalt ions in the mixed solution A is 0.06mol/L-0.30mol/L.
The volume ratio of the terephthalic acid in the step 2) to the dimethyl imidazole in the step 1) is 1.
The total molar ratio of the total mass of the metal salt ions to the mixed ligand is 1; the metal salt ions are nickel ions and cobalt ions; the mixed ligand is terephthalic acid and dimethyl imidazole.
In the step 3), the treatment mode of the activated carbon is as follows: and treating the activated carbon cloth with acetone and ethanol to remove surface grease.
In the step 3), the activated carbon cloth is 1cm multiplied by 2cm hydrophilic commercial carbon cloth, the thickness is 0.36mm, and the longitudinal resistance is less than 0.12 multiplied by 10 -2 Omega, formed by carbonizing preoxidized polyacrylonitrile fiber fabric, and has the characteristics of good conductivity, flexibility, large specific surface area and the like.
In the step 4), the reaction temperature of the hydrothermal reaction is 150-180 ℃, and the reaction time is 12-18 h.
In the step 5), the drying temperature is 80-100 ℃, and the drying time is 12-24 h.
The invention adopts a mild, low-energy-consumption, rapid and safe hydrothermal synthesis method, selects soluble nickel nitrate hexahydrate and cobalt nitrate hexahydrate as reactants, takes dimethylimidazole and terephthalic acid as mixed organic ligands, and obtains the nickel-cobalt bimetal organic framework crystal material which grows on the surface of the activated carbon cloth in a self-supporting way by adjusting reaction parameters.
The invention has the beneficial effects that:
1) The crystal with the wavy sheet structure prepared by the invention has uniform size distribution,Good crystallinity, uniform chemical composition, 0-0.6V in scanning window, and current density of 2mA/cm 2 In the process, the specific capacitance of the prepared NiCo-MOF composite electrode material reaches 834F/g, and the NiCo-MOF composite electrode material has high specific capacity and rate capability.
2) The invention takes carboxylic acid compounds terephthalic acid and dimethyl imidazole as mixed organic ligands:
the carboxylic acid compound terephthalic acid, also called p-phthalic acid, is a binary aromatic carboxylic acid formed by connecting two carboxyl groups with two opposite carbon atoms in a benzene ring respectively, and has the following two functions: firstly, as a first organic ligand, the terephthalic acid contains two diagonal carboxylic acid groups, the carboxylic acid groups can form a uniform network with nickel cobalt ions, and the uniform connection of the metal ions and the carboxylic acid groups leads to longer chain length and improves the surface area and the porosity; and secondly, the carboxylic acid group and the carbon-containing skeleton in the terephthalic acid can be bridged with the nitrogen-containing active site in the dimethylimidazole to effectively increase the coordination sites of the organic ligand and the metal ions, thereby increasing the redox active sites.
Dimethylimidazole has the following triple effects: firstly, the nickel and cobalt complex is used as a reaction solvent to promote the metal salt of nickel and cobalt and the organic ligand to be fully dissolved; secondly, the dimethyl imidazole molecule is used as a second organic ligand to react with metal ions, and two functional (nitrogen) sites of the dimethyl imidazole molecule can be coordinated with the metal ions to form a network; and thirdly, the coordination reaction is carried out with the first organic ligand terephthalic acid, carboxylic acid groups in the terephthalic acid and functional nitrogen groups in the dimethyl imidazole can form mixed coordination with metal ions so as to guide the micro arrangement of atoms, so that a uniform network structure can be formed by adjusting the molar ratio of the terephthalic acid to the dimethyl imidazole, and the bimetallic organic framework crystal obtained by coordination is synergistically influenced by the double ligands and has adjustable molecular morphology and structure. The synergistic effect of the double ligands forms a network structure, and a two-dimensional sheet shape is induced and generated. The sheet structure can increase the contact area of the electrode material and the electrolyte solution and accelerate the transmission of ions, thereby improving the performance, the preparation method is simple and easy to operate, and the electrode material is expected to be applied to the fields of novel electrode materials, catalysis, sensing and the like.
3) The invention takes the activated carbon cloth as the base material, the activated carbon cloth belongs to inert materials, and compared with other conductive substrates such as foamed nickel and the like, the activated carbon cloth has more flexibility, does not corrode or rust, is not easy to be corroded by harmful media, has good durability, and has more advantages in current conduction. The invention fully utilizes the porous structure on the fiber surface of the activated carbon cloth, can increase the contact area with the electrolyte, increase the pressure of the contact surface, reduce the contact resistance and other special functions, provides good conditions for the crystallization of metal organic framework crystals on the surface of the carbon cloth, and simultaneously utilizes the excellent conductivity of the activated carbon cloth to improve the defect of low conductivity of the metal organic framework material.
4) The invention takes polyvinylpyrrolidone as a surfactant, and because NiCo-MOF nano particles have small particle size and high surface energy and are easy to agglomerate, the polyvinylpyrrolidone is added and then wrapped on the surface of activated carbon cloth to block agglomeration and control the shape of the material, and the polyvinylpyrrolidone plays roles in dispersing ions and stabilizing.
Drawings
FIG. 1 is an XRD pattern of the product obtained in example 1.
FIG. 2 is an electron micrograph of the product obtained in example 1.
FIG. 3 is an electron micrograph of the product obtained in example 2.
FIG. 4 is an electron micrograph of the product obtained in example 3.
FIG. 5 is an electron micrograph of the product obtained in comparative example 1.
FIG. 6 is an electron micrograph of the product obtained in comparative example 2.
FIG. 7 is an electron micrograph of the product obtained in comparative example 3.
FIG. 8 is an electron micrograph of a product obtained in comparative example 4.
FIG. 9 is an electron micrograph of a product obtained in comparative example 5.
Detailed Description
The invention prepares the bimetallic organic framework crystal material which grows on the surface of the activated carbon cloth in a self-supporting way by using the double ligands. The activated carbon cloth is a common conductive base, has the function of a current collector material, has the characteristics of flexibility, large specific surface area and the like, can construct a composite electrode material by generating a metal organic framework on the surface of the activated carbon cloth in a self-supporting manner, and effectively improves the electrochemical performance of the electrode material. The synergy of the double ligands, the flaky shape of the crystal material, the design of the self-supporting structure and the construction of a binder-free system are all beneficial to improving the electrochemical performance.
The nickel-cobalt bimetallic organic framework crystal prepared by the method has a uniform sheet structure, the average thickness of the nickel-cobalt bimetallic organic framework crystal is 0.15-0.20 mu m, the sheet structure increases the contact area with electrolyte, and the ion transmission rate is accelerated, so that the performance is improved.
Example 1:
0.2910g of cobalt nitrate hexahydrate, 0.2910g of nickel nitrate hexahydrate and 0.1500g of terephthalic acid were dissolved in 30mL of a dimethylimidazole solution. 1.5000g of polyvinylpyrrolidone was added to the mixed solution, and stirred magnetically for 30min to obtain a homogeneous solution. And then immersing the treated activated carbon cloth into the mixed solution for ultrasonic treatment for 1h, pouring the uniformly mixed solution together with the activated carbon cloth into a 100mL reaction kettle, reacting for 12h at 150 ℃, after the reaction is finished, naturally cooling the reaction kettle to normal temperature, repeatedly and centrifugally cleaning the obtained activated carbon cloth with absolute ethyl alcohol and deionized water for three times, removing impurities such as surface adsorbed ions and attachments, and drying for 12h at 80 ℃ to obtain the flaky nickel-cobalt bimetallic organic framework crystal loaded on the activated carbon cloth.
FIG. 1 is an XRD pattern of the product of example 1, which is matched with a simulated NiCO-MOF (No. 638866) in a CCDC crystal library, and demonstrates that the in-situ growth on the surface of the activated carbon cloth is a nickel-cobalt bimetallic organic framework crystal, and diffraction peaks appearing between 20 degrees and 30 degrees at 2 theta correspond to crystal faces of graphite crystals (001) and (110), so that the hydrophilic commercial carbon cloth is of a graphite-like structure; FIG. 2 is an electron micrograph of the product of example 1, which shows that a uniform lamellar structure with a lamellar thickness of 100-200nm is formed on the surface of the activated carbon cloth.
Example 2:
0.5810g of cobalt nitrate hexahydrate, 0.5810g of nickel nitrate hexahydrate and 0.1500g of terephthalic acid were dissolved in 30mL of a dimethylimidazole solution. 1.5000g of polyvinylpyrrolidone was added to the mixed solution, and stirred magnetically for 30min to obtain a homogeneous solution. And then immersing the treated activated carbon cloth into the mixed solution for ultrasonic treatment for 1h, pouring the uniformly mixed solution together with the activated carbon cloth into a 100mL reaction kettle, reacting for 16h at 150 ℃, after the reaction is finished, naturally cooling the reaction kettle to normal temperature, repeatedly and centrifugally cleaning the obtained activated carbon cloth with absolute ethyl alcohol and deionized water for three times, removing impurities such as surface adsorbed ions and attachments, and drying at 80 ℃ for 12h to obtain the flaky nickel-cobalt bimetallic organic framework crystal loaded on the activated carbon cloth.
FIG. 3 is an electron micrograph of the product of example 2, wherein a uniform lamellar structure is formed on the surface of the activated carbon cloth, and the lamellar thickness is 100-150nm.
Example 3:
1.4530g of cobalt nitrate hexahydrate, 1.4530g of nickel nitrate hexahydrate and 0.1500g of terephthalic acid were dissolved in 30mL of a dimethylimidazole solution. And adding 1.5000g of polyvinylpyrrolidone into the mixed solution, and magnetically stirring for 30min to obtain a uniform solution. And then immersing the treated activated carbon cloth in the mixed solution for ultrasonic treatment for 1 hour, pouring the uniformly mixed solution together with the activated carbon cloth into a 100mL reaction kettle, reacting for 18 hours at 180 ℃, after the reaction is finished, naturally cooling the reaction kettle to normal temperature, repeatedly and centrifugally cleaning the obtained activated carbon cloth with absolute ethyl alcohol and deionized water for three times, removing impurities such as surface adsorbed ions and attachments, and drying for 12 hours at 80 ℃ to obtain the flaky nickel-cobalt bimetallic organic framework crystal loaded on the activated carbon cloth.
FIG. 4 is an electron micrograph of the product of example 3, wherein the surface of the activated carbon cloth forms a uniform lamellar structure with a lamellar thickness of 200-300nm.
Comparative example 1:
0.5810g of cobalt nitrate hexahydrate, 0.9880g of nickel nitrate hexahydrate and 0.1500g of terephthalic acid were dissolved in 30mL of a dimethylimidazole solution. 1.5000g of polyvinylpyrrolidone was added to the mixed solution, and stirred magnetically for 30min to obtain a homogeneous solution. And then immersing the treated activated carbon cloth in the mixed solution for ultrasonic treatment for 1h, pouring the uniformly mixed solution together with the activated carbon cloth into a 100mL reaction kettle, reacting for 18h at 180 ℃, after the reaction is finished, naturally cooling the reaction kettle to normal temperature, repeatedly centrifuging and cleaning the obtained activated carbon cloth with absolute ethyl alcohol and deionized water for three times, removing impurities such as surface adsorbed ions and attachments, and drying for 12h at 80 ℃ to obtain a final product.
FIG. 5 is an electron micrograph of the product of comparative example 1, in which the activated carbon cloth had an amorphous shape without forming a lamellar structure on the surface.
Comparative example 2:
0.5810g of cobalt nitrate hexahydrate, 0.5810g of nickel nitrate hexahydrate and 0.5000g of terephthalic acid were dissolved in 30mL of a dimethylimidazole solution. And adding 1.5000g of polyvinylpyrrolidone into the mixed solution, and magnetically stirring for 30min to obtain a uniform solution. And then immersing the treated activated carbon cloth in the mixed solution for ultrasonic treatment for 1h, pouring the uniformly mixed solution together with the activated carbon cloth into a 100mL reaction kettle, reacting for 12h at 150 ℃, after the reaction is finished, naturally cooling the reaction kettle to normal temperature, repeatedly centrifuging and cleaning the obtained activated carbon cloth for three times by using absolute ethyl alcohol and deionized water, removing impurities such as surface adsorbed ions and attachments, and drying for 12h at 80 ℃ to obtain a final product.
FIG. 6 is an electron micrograph of the product of comparative example 2, in which the activated carbon cloth had no lamellar structure but had an amorphous shape on the surface.
Comparative example 3:
0.5810g of cobalt nitrate hexahydrate, 0.581g of nickel nitrate hexahydrate and 0.15g of terephthalic acid were dissolved in 30mL of a dimethylimidazole solution, 1.5000g of polyvinylpyrrolidone was added to the mixed solution, and the mixture was magnetically stirred for 30min to obtain a uniform solution. And then immersing the treated activated carbon cloth in the mixed solution for ultrasonic treatment for 1h, pouring the uniformly mixed solution together with the activated carbon cloth into a 100mL reaction kettle, reacting for 8h at 120 ℃, after the reaction is finished, naturally cooling the reaction kettle to normal temperature, repeatedly centrifuging and cleaning the obtained activated carbon cloth with absolute ethyl alcohol and deionized water for three times, removing impurities such as surface adsorbed ions and attachments, and drying for 12h at 80 ℃ to obtain a final product.
FIG. 7 is an electron micrograph of the product of comparative example 3, in which the activated carbon cloth had no lamellar structure but had an amorphous shape on the surface.
Comparative example 4:
0.5810g of cobalt nitrate hexahydrate, 0.581g of nickel nitrate hexahydrate and 0.15g of terephthalic acid were dissolved in 30mL of a dimethylimidazole solution, and the mixture was magnetically stirred for 30min to obtain a uniform solution. And then immersing the treated activated carbon cloth in the mixed solution for ultrasonic treatment for 1 hour, pouring the uniformly mixed solution together with the activated carbon cloth into a 100mL reaction kettle, reacting for 12 hours at 150 ℃, after the reaction is finished, naturally cooling the reaction kettle to normal temperature, repeatedly and centrifugally cleaning the obtained activated carbon cloth with absolute ethyl alcohol and deionized water for three times, removing impurities such as surface adsorption ions and attachments, and drying for 12 hours at 80 ℃ to obtain a final product.
FIG. 8 is an electron micrograph of the product of comparative example 4, in which the activated carbon cloth had no lamellar structure but had an amorphous shape on the surface.
Comparative example 5:
0.5810g of cobalt nitrate hexahydrate and 0.581g of nickel nitrate hexahydrate are dissolved in 30mL of dimethyl imidazole solution, 1.5000g of polyvinylpyrrolidone is added into the mixed solution, and the mixture is magnetically stirred for 30min to obtain a uniform solution. And then immersing the treated activated carbon cloth in the mixed solution for ultrasonic treatment for 1 hour, pouring the uniformly mixed solution together with the activated carbon cloth into a 100mL reaction kettle, reacting for 12 hours at 150 ℃, after the reaction is finished, naturally cooling the reaction kettle to normal temperature, repeatedly and centrifugally cleaning the obtained activated carbon cloth with absolute ethyl alcohol and deionized water for three times, removing impurities such as surface adsorption ions and attachments, and drying for 12 hours at 80 ℃ to obtain a final product.
FIG. 9 is an electron micrograph of the product of comparative example 5, in which the activated carbon cloth had no lamellar structure but had an amorphous shape on the surface.
Claims (10)
1. A flaky nickel-cobalt bimetallic organic framework crystal material is characterized in that dimethyl imidazole and terephthalic acid are used as mixed organic ligands, nickel nitrate hexahydrate and cobalt nitrate hexahydrate are used as reactants, and a flaky nickel-cobalt bimetallic organic framework crystal loaded on the surface of active carbon cloth is obtained through a hydrothermal reaction;
the nickel-cobalt bimetallic organic framework crystals exhibit a uniform lamellar structure with an average thickness of 0.15 to 0.20. Mu.m.
2. The method of preparing a sheet-like nickel-cobalt bimetallic organic framework crystalline material of claim 1, comprising the steps of:
1) Dissolving nickel nitrate hexahydrate and cobalt nitrate hexahydrate in a dimethyl imidazole solvent, and uniformly stirring to obtain a mixed solution A;
2) Adding terephthalic acid and polyvinylpyrrolidone into the mixed solution A, and continuously stirring to obtain a mixed solution B;
3) Soaking the treated activated carbon cloth in the mixed solution B for ultrasonic treatment for 1h;
4) Carrying out hydrothermal reaction on the solution obtained in the step 3) and the activated carbon cloth in a reaction kettle;
5) Naturally cooling the reaction kettle after the reaction in the step 4) to normal temperature, repeatedly cleaning the reaction kettle with absolute ethyl alcohol and deionized water for three times, and drying to obtain the flaky nickel-cobalt bimetallic organic framework crystal uniformly grown on the surface of the activated carbon cloth.
3. The method according to claim 2, wherein in the step 1),
the molar mass ratio of the nickel nitrate hexahydrate to the cobalt nitrate hexahydrate is 1;
the molar concentration of the dimethyl imidazole solvent is 0.2mol/L, and the dosage is 30mL.
4. The production method according to claim 2, wherein in the step 1), the total molar concentration of the nickel ions and the cobalt ions in the mixed solution a is 0.06mol/L to 0.30mol/L.
5. The method according to claim 2, wherein the volume ratio of terephthalic acid in step 2) to dimethylimidazole in step 1) is 1.
6. The preparation method according to claim 2, wherein the ratio of the total amount of metal salt ions to the total molar amount of mixed ligands is 1;
the metal salt ions are nickel ions and cobalt ions;
the mixed ligand is terephthalic acid and dimethyl imidazole.
7. The method according to claim 2, wherein the activated carbon is treated in the step 3) in such a manner that: and treating the activated carbon cloth with acetone and ethanol to remove surface grease.
8. The production method according to claim 2, wherein in the step 3), the activated carbon cloth longitudinal resistance is less than 0.12 x 10 -2 Omega, formed by carbonizing pre-oxidized polyacrylonitrile fiber fabric.
9. The preparation method according to claim 2, wherein in the step 4), the reaction temperature of the hydrothermal reaction is 150-180 ℃, and the reaction time is 12-18 h.
10. The preparation method according to claim 2, wherein in the step 5), the drying temperature is 80-100 ℃ and the drying time is 12-24 h.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104088016A (en) * | 2014-07-03 | 2014-10-08 | 浙江理工大学 | One-dimensional NiCo2S4 crystal array on surface of activated carbon fiber and preparation method of one-dimensional NiCo2S4 crystal array |
| CN107195875A (en) * | 2017-04-26 | 2017-09-22 | 复旦大学 | A kind of three-dimensional grapheme cladding MOF composite electrode material and preparation method thereof |
| CN110283333A (en) * | 2019-07-31 | 2019-09-27 | 商丘师范学院 | A kind of double ligand Zn complexes of three-dimensional layer pole structure and preparation method thereof |
| CN110610816A (en) * | 2019-09-18 | 2019-12-24 | 江苏大学 | Preparation method of carbon cloth-based nickel-cobalt double-metal selenide nano square sheet electrode material |
| CN112670093A (en) * | 2020-12-08 | 2021-04-16 | 宁波大学 | Porous Co3O4@ Ni-MOF core-shell structure nanosheet array material and preparation method and application thereof |
| CN112837943A (en) * | 2021-04-22 | 2021-05-25 | 中国科学院过程工程研究所 | Ultrathin two-dimensional nanosheet layer NiCo-MOF material, and preparation method and application thereof |
| US20210155649A1 (en) * | 2018-10-09 | 2021-05-27 | Soochow University | Ultra-thin ni-fe-mof nanosheet, preparation method and use thereof |
| CN113000067A (en) * | 2021-01-12 | 2021-06-22 | 山东科技大学 | Bimetallic mixed ligand metal organic framework photocatalyst and preparation method thereof |
| CN114031784A (en) * | 2021-10-21 | 2022-02-11 | 上海应用技术大学 | Method for preparing nickel-cobalt bimetal organic framework composite material and application |
| CN115028847A (en) * | 2022-05-09 | 2022-09-09 | 复旦大学 | CoNi alloy MOF porous material and preparation and application thereof |
-
2022
- 2022-11-22 CN CN202211467637.2A patent/CN115725084A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104088016A (en) * | 2014-07-03 | 2014-10-08 | 浙江理工大学 | One-dimensional NiCo2S4 crystal array on surface of activated carbon fiber and preparation method of one-dimensional NiCo2S4 crystal array |
| CN107195875A (en) * | 2017-04-26 | 2017-09-22 | 复旦大学 | A kind of three-dimensional grapheme cladding MOF composite electrode material and preparation method thereof |
| US20210155649A1 (en) * | 2018-10-09 | 2021-05-27 | Soochow University | Ultra-thin ni-fe-mof nanosheet, preparation method and use thereof |
| CN110283333A (en) * | 2019-07-31 | 2019-09-27 | 商丘师范学院 | A kind of double ligand Zn complexes of three-dimensional layer pole structure and preparation method thereof |
| CN110610816A (en) * | 2019-09-18 | 2019-12-24 | 江苏大学 | Preparation method of carbon cloth-based nickel-cobalt double-metal selenide nano square sheet electrode material |
| CN112670093A (en) * | 2020-12-08 | 2021-04-16 | 宁波大学 | Porous Co3O4@ Ni-MOF core-shell structure nanosheet array material and preparation method and application thereof |
| CN113000067A (en) * | 2021-01-12 | 2021-06-22 | 山东科技大学 | Bimetallic mixed ligand metal organic framework photocatalyst and preparation method thereof |
| CN112837943A (en) * | 2021-04-22 | 2021-05-25 | 中国科学院过程工程研究所 | Ultrathin two-dimensional nanosheet layer NiCo-MOF material, and preparation method and application thereof |
| CN114031784A (en) * | 2021-10-21 | 2022-02-11 | 上海应用技术大学 | Method for preparing nickel-cobalt bimetal organic framework composite material and application |
| CN115028847A (en) * | 2022-05-09 | 2022-09-09 | 复旦大学 | CoNi alloy MOF porous material and preparation and application thereof |
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