CN106710884B - metal-organic complex and silver nanowire complex as well as preparation method and application thereof - Google Patents
metal-organic complex and silver nanowire complex as well as preparation method and application thereof Download PDFInfo
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- CN106710884B CN106710884B CN201611023788.3A CN201611023788A CN106710884B CN 106710884 B CN106710884 B CN 106710884B CN 201611023788 A CN201611023788 A CN 201611023788A CN 106710884 B CN106710884 B CN 106710884B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—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
Abstract
The invention provides a metal-organic complex and silver nanowire complex, which is a two-dimensional sheet structure and comprises silver nanowires, organic ligands and metal salts in a molar ratio of 1 (2-4) to (1-3). The invention also provides a preparation method and application of the metal-organic complex and silver nanowire complex. The compound has the advantages of simple preparation process, short reaction time, high repetition rate, easy reaction, high efficiency, low energy consumption and low cost.
Description
Technical Field
The invention belongs to the technical field of new energy and supercapacitors, and particularly relates to a metal-organic complex and silver nanowire compound, and a preparation method and application of the compound.
Background
In order to meet the huge demand of movable new energy, the super capacitor with excellent performance, safety, low price and environmental friendliness has attracted the extensive attention of related enterprises and experts in the industry. The super capacitor can be classified into 3 types such as a pseudo capacitor, a double-layer capacitor and a hybrid capacitor according to different energy storage mechanisms, and the electrode material of the super capacitor can also be classified into 3 types such as a carbon material, a metal oxide (such as RuO2) and a conductive polymer (such as polypyridine (PPy), Polyacrylonitrile (PAN) and the like). The metal oxide and the conductive polymer mainly generate pseudo capacitance, and the carbon material mainly forms electric double layer capacitance. The combination of two of the 3 types of electrode materials to form a hybrid capacitor has become a current research trend.
Because the cobalt-based MOFs have the advantages of gas absorption, high functional density and good cycle stability, the cobalt-based MOFs are gradually explored and applied in the field of supercapacitors; the silver nanowires are used as excellent conductive materials and are consistent with MOFs materials with high capacitance, and the formed composite material integrates high capacitance and high conductivity, so that the silver nanowires are very important in the field of supercapacitors. However, in general, the composite material, especially the composite material having a high specific surface area to a substrate, is difficult to perform without a series of methods of supplying energy thereto such as hydrothermal treatment, and thus a metal-organic complex and a silver nanowire complex have not been reported.
Disclosure of Invention
The technical problem is as follows: in order to solve the defects of the prior art, the invention provides a metal-organic complex and silver nanowire compound as well as a preparation method and application thereof.
The technical scheme is as follows: the metal-organic complex and silver nanowire complex provided by the invention is a two-dimensional sheet structure and comprises silver nanowires, organic ligands and metal salts in a molar ratio of 1 (2-4) to (1-3).
The invention also provides a preparation method of the metal-organic complex and silver nanowire complex, which comprises the following steps: under the condition of stirring at room temperature, sequentially adding the silver nanowire ethanol solution, the organic ligand and the metal salt into a reaction solvent, stirring at room temperature for coprecipitation, centrifuging, washing the precipitate, and drying to obtain the metal-organic complex and silver nanowire complex.
The silver nanowires are prepared by adopting a polyol reduction method.
Wherein the reaction solvent is a mixed solvent of monohydric alcohol of (1-3) and water, and the monohydric alcohol is preferably methanol or ethanol; the organic ligand is dimethyl imidazole, benzimidazole, trimesic acid or gamma-cyclodextrin; the metal salt is soluble cobalt salt, copper salt, zinc salt or potassium salt; the molar ratio of the silver nanowires to the organic ligand to the metal salt is 1 (2-4) to 1-3.
Wherein the coprecipitation time is 4-6 h.
The invention also provides application of the metal-organic complex and the silver nanowire complex in a super capacitor.
Has the advantages that: the compound provided by the invention has the advantages of simple preparation process, short reaction time, high repetition rate, easiness in reaction, high efficiency, low energy consumption and low cost.
the silver nanowires are used as carriers and dispersed in an ethanol solution, the silver nanowires have excellent optical and electrical properties, however, the surfaces of the silver nanowires are smooth, the silver nanowires are free of any group modification and are difficult to be compounded with metal salts, the metal salts are compounded with the silver nanowires under the condition that no modification is carried out at room temperature, and the prepared flaky MOFs and silver nanowire composite material has a two-dimensional structure, has a large specific surface area, is beneficial to electronic transmission, and has excellent performance and potential application value according to electrochemical tests.
In particular, the present invention has the following outstanding advantages over the prior art:
(1) The composite provided by the invention adopts MOFs and silver nanowires to form a sheet-shaped composite structure, the structure combines the advantages of the MOFs and the silver nanowires, the defects of instability and easiness in oxidation of silver are overcome, and the capacitance effect is better.
(2) The metal-organic complexes (MOFs) recognized before are three-dimensional structures, while the metal-organic complexes and the silver nanowire complexes disclosed by the invention are two-dimensional structures, have large specific surface areas, are beneficial to the transmission of electron ions, and have higher capacitance than the conventional MOFs. The composite material of the sheet MOFs and the silver nanowires disclosed by the invention is not reported at present.
(3) In the preparation method of the compound, the silver nanowires are added before the MOFs are formed, the formed sheet structure can interact with the silver nanowires, when the MOFs is formed by crystallizing metal ions and ligands, the nanowires can be well wrapped in the MOFs sheet structure, and the nanowires penetrate and wrap in the MOFs film, so that the conductivity of the material is improved, and the capacitance is increased.
(4) The preparation method of the compound has simple process: firstly, the metal-organic complex and the silver nanowire complex are synthesized by stirring at room temperature, so that the method is simple and convenient, the steps are simple, and the repetition rate can reach one hundred percent; secondly, the synthesized product does not need vacuum drying, only needs room temperature drying or airing, and is simple and easy to operate; the method has the advantages of good implementability, simple operation, low price and good practicability.
(5) The leading research on the development of advanced energy storage devices is the need to address a sustainable future, with nanomaterials having a broad application prospect due to their large surface to volume ratio, good transport properties and attractive physicochemical properties.The invention successfully synthesizes the two-dimensional amorphous metal-organic complex (Cozif)/silver nanowire (AgNWs) nanosheet by stirring in the solution at room temperature, and the electrochemical test experimental data show that: the two-dimensional system structure provided by the invention not only provides enough active materials to be in contact with the electrolyte, but also promotes the transmission of ions and electrons and buffers volume change on the basis of a two-electrode system and circulation stability, and provides high specific capacitance. As an electrode material of a super capacitor, the composite provided by the invention is placed in a 3M potassium hydroxide aqueous solution for detection, and 1.0Ag-1Has a capacitance up to 1497Fg at a current density of-1。
Drawings
FIG. 1 is a scanning electron micrograph of a plate-like ZIF-67 product of a comparative example.
FIG. 2 SEM and TEM images of the composite material of the plate-like ZIF-67 and silver nanowires in example 1.
FIG. 3 Infrared profiles of ZIF-67, ZIF-67/silver nanowire complexes in example 1 and comparative example.
Detailed Description
In the present invention, the length of the silver nanowire used is not required, and the silver nanowire with the desired crystal form and diameter can be prepared by the methods disclosed in the prior art, for example, the silver nanowire can be prepared by the methods disclosed in the following documents:
(1)Changchao Jia,Ping Yang,Aiyu Zhang.Glycerol and ethylene glycol co-mediated synthesis of uniform multiple crystalline silver nanowires,Materials Chemistry and Physics,2014,143(2),794-800.
(2)Linfeng Gou,Mircea Chipara,and Jeffrey M.Zaleski,Convenient,Rapid Synthesis of Ag Nanowires,Chem.Mater.2007,19,1755-1760.
(3)Yugang Sun,Yadong Yin,Brian T.Mayers,Thurston Herricks,and Younan Xia,Uniform Silver Nanowires Synthesis by Reducing AgNO3with Ethylene Glycolin the Presence of Seeds and Poly(Vinyl Pyrrolidone).Chem.Mater.2002,14,4736-4745.
The present invention is further described below by way of examples, but the embodiments of the present invention are not limited thereto.
Comparative example preparation of flaky ZIF-67
9ml of methanol and 9ml of deionized water were used as a solvent for the reaction, and 0.9mmol of dimethylimidazole (2-methylimidazole) and 0.6mmol of cobalt nitrate hexahydrate (Co (NO) were added thereto under stirring at room temperature3)2·6H2O), stirring for 5 hours at room temperature, centrifuging, washing, and drying at room temperature to obtain the flaky ZIF-67, wherein the scanning electron microscope experiment result of the product is shown in figure 1, and the infrared ray is shown in figure 3.
Example 1
The metal-organic complex and silver nanowire complex (ZIF-67) is of a two-dimensional sheet structure and comprises silver nanowires, organic ligands and metal salts in a molar ratio of 1:3: 2.
The preparation method comprises the following steps: 9ml of methanol and 9ml of deionized water were used as a solvent for the reaction, and 0.9mmol of dimethylimidazole (2-methylimidazole) was added thereto, followed by addition of 0.3mmol of an ethanol solution of silver nanowires and addition of 0.6mmol of cobalt nitrate hexahydrate (Co (NO) (NO: Co) with stirring at room temperature3)2·6H2O), stirring for 5 hours at room temperature, centrifuging, washing and drying at room temperature to obtain the product. The experimental results of the scanning electron microscope and the transmission electron microscope of the product are shown in figure 2, and the infrared ray is shown in figure 3.
The formed sheet-shaped composite material of the MOFs and the silver nanowires is easy to bend into folds; the sheet structure formed by the MOFs can interact with the silver nanowires, when metal ions and ligands are crystallized to form the MOFs, the nanowires can be well wrapped in the sheet structure of the MOFs, and the nanowires penetrate through and wrap in the MOFs membrane. The metal-organic complex and the silver nanowire complex are micron-sized and have good electrochemical performance.
Example 2
The metal-organic complex and silver nanowire complex (ZIF-67) is a two-dimensional sheet structure and comprises silver nanowires, organic ligands and metal salts in a molar ratio of 1:2: 1.
The preparation method comprises the following steps: and taking 9ml of methanol and 9ml of deionized water as solvents for reaction, adding 0.6mmol of benzimidazole under stirring at room temperature, then adding 0.3mmol of ethanol solution of silver nanowires, then adding 0.3mmol of zinc nitrate, stirring for 5 hours at room temperature, centrifuging, washing, and drying at room temperature to obtain the silver nanowire/zinc nitrate/zinc nanowire composite material.
Example 3
The metal-organic complex and silver nanowire complex (ZIF-67) is of a two-dimensional sheet structure and comprises silver nanowires, organic ligands and metal salts in a molar ratio of 1:4: 3.
The preparation method comprises the following steps: and taking 9ml of methanol and 27ml of deionized water as solvents for reaction, adding 1.2mmol of trimesic acid under stirring at room temperature, then adding 0.3mmol of silver nanowire methanol solution, then adding 0.9mmol of copper chloride, stirring for 4 hours at room temperature, centrifuging, washing, and drying at room temperature to obtain the silver nanowire nano-silver nanoparticle.
Example 4
The metal-organic complex and silver nanowire complex (ZIF-67) is of a two-dimensional sheet structure and comprises silver nanowires, organic ligands and metal salts in a molar ratio of 1:3: 2.
The preparation method comprises the following steps: taking 27ml of methanol and 9ml of deionized water as solvents for reaction, adding 0.9mmol of gamma-cyclodextrin while stirring at room temperature, then adding 0.3mmol of ethanol solution of silver nanowires, then adding 0.6mmol of potassium nitrate, stirring at room temperature for 6 hours, centrifuging, washing, and drying at room temperature to obtain the silver nanowire/silver nanowire composite material.
Claims (5)
- A MOFs and silver nanowire complex characterized by: the compound is a two-dimensional sheet structure, the prepared raw materials comprise silver nanowires, organic ligands and metal salts in a molar ratio of 1 (2-4) to (1-3), and the preparation method of the MOFs and silver nanowire compound comprises the following steps: and under the condition of stirring at room temperature, sequentially adding the silver nanowire ethanol solution, the organic ligand and the metal salt into the reaction solvent, stirring at room temperature for coprecipitation, centrifuging, washing the precipitate, and drying to obtain the MOFs and silver nanowire compound.
- 2. The MOFs and silver nanowire composites of claim 1, wherein: the silver nanowires are prepared by adopting a polyol reduction method.
- 3. The MOFs and silver nanowire composites of claim 1, wherein: the reaction solvent is a mixed solvent of monohydric alcohol and water of (1-3) and (1-3), and the monohydric alcohol is methanol or ethanol; the organic ligand is dimethyl imidazole, benzimidazole, trimesic acid or gamma-cyclodextrin; the metal salt is soluble cobalt salt, copper salt, zinc salt or potassium salt; the molar ratio of the silver nanowires to the organic ligand to the metal salt is 1 (2-4) to 1-3.
- 4. The MOFs and silver nanowire composites of claim 1, wherein: coprecipitation is carried out for 4-6 h.
- 5. Use of the MOFs and silver nanowire composites of claim 1 in supercapacitors.
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| CN107867713B (en) * | 2017-11-09 | 2019-07-05 | 扬州大学 | A kind of ZnO sensing electrode material preparation method of porous nano pie structure |
| CN108213414B (en) * | 2017-12-29 | 2020-04-21 | 安庆师范大学 | Method for improving light stability of gold nanoclusters by coating MOF and application of method |
| CN110137461A (en) * | 2019-05-10 | 2019-08-16 | 陕西科技大学 | Lithium ion battery cobalt/cobalt oxide carbon nano-fiber flexible electrode material and preparation method thereof derived from MOF |
| CN110527107A (en) * | 2019-08-27 | 2019-12-03 | 深圳大学 | A kind of orderly two-dimentional electroconductive molecule monolayer array preparation method and photoelectric device |
| CN111234245A (en) * | 2020-01-15 | 2020-06-05 | 扬州大学 | Ag nanowire/ZIF ultrathin nanosheet composite material, preparation method and application |
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