CN114957699B - Cu-MOF-based friction nano power generation material and preparation method and application thereof - Google Patents
Cu-MOF-based friction nano power generation material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Cu-MOF-based friction nano power generation material, a preparation method and application thereof, wherein the friction nano power generation material comprises three water phasesCopper nitrate, 1' - [1, 4-phenylenedi (methylene)]Sealing the mixture of the bis (3, 5-dicarboxypyridine), the azo bis (2-pyridine), the N, N-dimethylformamide and water in a glass bottle, and fully vibrating in an ultrasonic cleaner for five minutes until the mixture is completely dissolved; placing the mixture in a baking oven at 90 ℃ for reaction for 24 hours; and cooling to room temperature to obtain green blocky crystals, washing with mother liquor, and drying to obtain the Cu-MOF-based friction nano power generation material. The application of the composite material in the vertical contact separation type friction nano generator Cu-MOF-TENG shows excellent output performance and cycle stability, and the charge density and the power density can reach 135.64 mu C.m ‑2 And 9841.50mW m ‑2 Higher than the reported complex friction power generation materials.
Description
Technical Field
The invention belongs to the technical field of friction power generation materials, and particularly relates to a Cu-MOF-based friction nano power generation material, and a preparation method and application thereof.
Background
With the excessive use of fossil energy, people face a huge energy crisis. The development of numerous renewable energy sources has many problems, such as being influenced by the environment and weather during the process of collecting solar energy, wave energy and wind energy, and the energy conversion efficiency is low. The tribo-nano-generator (Triboelectric nanogenerator, TENG) can fully convert energy neglected in the environment into electrical energy through a coupling of triboelectrification and electrostatic induction. Due to the small size, the friction nano generator is easy to prepare and is very suitable for supplying power to electronic equipment. However, the presently reported triboelectric power generation materials have difficulty meeting the demands of self-powered sensors of high stability, high efficiency and versatility. Therefore, it is of great importance to design and develop triboelectric materials with excellent output performance and cycling stability. Metal Organic Frameworks (MOFs) materials have been found to have the output properties of friction nano generators and to play an important practical role in energy storage, catalysis and corrosion protection. MOFs have functional frameworks and open channels that can lead to higher output performance and complex functional diversity compared to polymer insulating electrolyte materials such as poly (tetrafluoroethylene). Therefore, the new metal organic frame material is synthesized and developed into the triboelectric material with high performance, low cost, good repeatability and durability, and has important practical application significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a crystalline MOF material with high vertical contact separation type friction power generation performance and strong stability. The invention utilizes 1,1' - [1, 4-phenylene bis (methylene) ] bis (3, 5-dicarboxypyridine) and azo bis (2-pyridine) as organic ligands. Meanwhile, the material is also used as an electrode material of the vertical contact separation type friction nano generator.
In order to solve the technical problems, the invention adopts the following technical scheme:
a friction nano power generation material based on Cu-MOF (metal oxide semiconductor field effect transistor), which is a crystalline MOF material and has a molecular structure of { [ CuC ] 21 H 18 N 6 O 9 } n Where n= infinity.
The friction nano power generation material is monoclinic system, and the space group P2 1 N, unit cell parameters are
α=90, β= 90.685 (2), γ=90, the smallest structural unit of which consists of 1 copper ion, 0.5 1,1' - [1, 4-phenylenedi (methylene)]Bis (3, 5-dicarboxypyridine) and 1 azopyridine molecule.
The synthetic method of the friction nano power generation material based on Cu-MOF comprises the following steps:
(1) Sealing a mixture of copper nitrate trihydrate, 1' - [1, 4-phenylenedi (methylene) ] bis (3, 5-dicarboxylpyridine), azobis (2-pyridine), N-dimethylformamide and water in a glass bottle, and fully vibrating for five minutes in an ultrasonic cleaner until the mixture is completely dissolved;
(2) Placing the mixture in a baking oven at 90 ℃ for reaction for 24 hours;
(3) And cooling to room temperature at a speed of 10 ℃/h to obtain green blocky crystals, washing with mother liquor, and drying to obtain the Cu-MOF-based friction nano power generation material.
Further, in the step (1), the molar ratio of copper nitrate trihydrate, 1' - [1, 4-phenylene bis (methylene) ] bis (3, 5-dicarboxypyridine) and azo bis (2-pyridine) is 10:2:5, and the volume ratio of N, N-dimethylformamide to water is 1:1.
The application of the friction nano power generation material based on Cu-MOF in the vertical contact separation type friction nano power generator comprises the following steps: the Cu-MOF was used to construct a friction nano generator Cu-MOF-TENG. And the polyvinylidene fluoride material is used as a counter electrode, and test experiments are carried out on the current, the charge density, the electric power density, the charging condition of a capacitor and the lighting condition of an LED lamp of the Cu-MOF-TENG, so that the result shows that the Cu-MOF can be used as a friction nano power generation material, and the mechanical energy can be effectively utilized.
The present invention uses copper sheets and Kapton films as the conductive layer and the charge storage layer, respectively, and crystalline powder materials (Cu-MOF based tribo nano-generating materials) and polyvinylidene fluoride as the friction layer. The Cu-MOF-TENG electrode material provided by the invention is excellent in performance and good in stability. Under the working conditions of vertical contact separation mode and 5Hz, the charge density and the power density can reach 135.64 mu C.m -2 And 9841.50mW m -2 . The short-circuit current reaches 109.32 mu A and can maintain a stable output state within 10000s, thus laying a foundation for commercial application. Meanwhile, the Cu-MOF-TENG can light 500 commercial LED lamps under the condition of 5Hz operation.
Compared with the prior art, the invention has the following beneficial effects:
1. the Cu-MOF is prepared by a common hydrothermal method process, the preparation method is simple and easy to operate, the mass production is easier, the cost is reduced, a new choice is provided for the friction nano power generation material, and the application value of the crystalline MOF material is expanded;
2. the Cu-MOF-TENG of the invention is connected verticallyUnder the operation conditions of the touch separation mode and 5Hz, the charge density and the power density can reach 135.64 mu C.m -2 And 9841.50mW m -2 The friction-electricity generating performance is higher than that of other materials which have been reported.
3. The Cu-MOF-TENG electrode material has good stability, can maintain a stable output state at 10000s, and lays a foundation for commercial application.
Drawings
FIG. 1 is a schematic representation of the molecular formula of 1,1' - [1, 4-phenylenedi (methylene) ] bis (3, 5-dicarboxypyridine) ligands used in material preparation.
FIG. 2 is a schematic representation of the molecular formula of an azobis (2-pyridine) ligand used in material preparation.
FIG. 3 is a structural diagram of the crystalline material Cu-MOF of example 1.
FIG. 4 is an X-ray powder diffraction pattern of the crystalline material Cu-MOF of example 1.
FIG. 5 is a thermogram of the crystalline material Cu-MOF of example 1.
FIG. 6 is an ultraviolet view of the crystalline material Cu-MOF of example 1.
FIG. 7 is a graph of Cu-MOF-TENG shorting current at 5Hz operation.
FIG. 8 is a graph of Cu-MOF-TENG charge density at 5Hz operation.
FIG. 9 is a 100. Mu.F time chart of Cu-MOF-TENG charging at 5Hz operation.
FIG. 10 is a graph of Cu-MOF-TENG electrical power density test at 5Hz operation.
FIG. 11 is a graph of Cu-MOF-TENG lighting 500 LED lamps at 5Hz operation.
FIG. 12 Cu-MOF-TENG short circuit current cycling stability at 5Hz operation.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Example 1
The preparation method of the friction nano power generation material based on Cu-MOF in the embodiment comprises the following steps:
copper nitrate hexahydrate (CuNO) 3 ·3H 2 O) (0.0242 g, 0.1 mmol), 1' - [1, 4-phenylenebis (methylene)]Bis (3, 5-dicarboxypyridine) (C) 22 H 18 N 2 O 8 ) (0.0100 g, 0.02 mmol), azobis (2-pyridine) (C 10 H 8 N 4 ) (0.0100 g, 0.05 mmol), N-dimethylformamide (3 ml), and H 2 The mixture of O (3 ml) was sealed in a 10 ml glass bottle and thoroughly shaken in an ultrasonic cleaner for five minutes until completely dissolved, and then placed in an oven at 90℃for reaction for 24 hours. And (3) cooling to room temperature at a speed of 10 ℃/h to obtain green blocky crystals, washing with mother liquor, and drying to obtain the target product Cu-MOF.
The crystal structure was measured by single crystal X-ray diffractometer as shown in figure 2.
The crystallographic parameters of Cu-MOF are detailed in the following table.
The crystalline material Cu-MOF was crushed and placed in a mortar for 0.5h to obtain a uniform powder. And a PANalytical X' Pert PRO powder single crystal diffractometer is adopted, and a powder X-ray diffraction pattern is obtained through Cu-K alpha ray radiation and test for 5 min. As shown in FIG. 4, the powder X-ray diffraction pattern obtained by the test was consistent with the peak position of the theoretical pattern, which indicates that the Cu-MOF obtained in example 1 was high in phase purity and could maintain a good crystalline state.
2. Thermogravimetric analysis of crystalline material Cu-MOF
The dried Cu-MOF material was placed in a Netzsch STA 449C thermal analyzer, air was vented, and thermogravimetric analysis was performed at a heating rate of 10℃min. As shown in FIG. 5, the Cu-MOF remained stable at 250℃which illustrates the wide temperature window of the Cu-MOF obtained in example 1.
3. Ultraviolet analysis of crystalline material Cu-MOF
The dried Cu-MOF material was placed in a mortar and ground for 0.5h to give a uniform powder. And testing with Lambda-950 ultraviolet-visible spectrophotometer, and selecting 250-800nm wavelength to obtain ultraviolet-visible spectrum. As shown in FIG. 6, the Cu-MOF has strong absorption peaks at 332nm and 668nm, which indicates that the Cu-MOF obtained in example 1 has an ultraviolet absorption characteristic peak of a typical copper coordination polymer.
Example 2
The application of the friction nano power generation material based on Cu-MOF in the vertical contact separation type friction nano power generator comprises the following steps: the Cu-MOF was used to construct a friction nano generator Cu-MOF-TENG. Using a copper sheet and a Kapton film as a conductive layer and a charge storage layer, respectively, a crystalline powder material (Cu-MOF-based friction nano-generating material) and polyvinylidene fluoride as a friction layer; and the polyvinylidene fluoride material is used as a counter electrode, and test experiments are carried out on the current, the charge density, the electric power density, the charging condition of a capacitor and the lighting condition of an LED lamp of the Cu-MOF-TENG, so that the result shows that the Cu-MOF can be used as a friction nano power generation material, and the mechanical energy can be effectively utilized.
The assembly process of Cu-MOF-TENG is as follows: the friction nano power generation material Cu-MOF prepared in example 1 was used, crushed Cu-MOF powder was coated on a copper sheet of 5cm×5cm, a copper sheet of 5cm×6cm was adhered to a counter electrode as a conductive layer, and copper wires were fixed to the copper sheets with conductive silver epoxy resin, respectively.
1. Short-circuit current test of prepared Cu-MOF friction nano generator
Under the room temperature environment, the mechanical energy with different frequencies is simulated by using a SUTP type voice coil motor of ten thousands to motor manufacturing company. And two copper wires are respectively connected to two ends of an SR570 type low-noise current amplifier produced by Stanford Research System company to collect short-circuit current signals. The charge density per unit area sigma is integrated by a curve of time and current at 5Hz operation
And (5) calculating to obtain the product.
2. Charging test of capacitor by prepared Cu-MOF friction nano generator
The mechanical energy at 5Hz frequency was simulated with a model SUTP voice coil motor of model ten thousand up to motor manufacturing limited under room temperature environment. And then the two copper wires are respectively connected to a rectifier to integrate the alternating current into direct current. Finally, the leads on the rectifier are respectively connected with two ends of an electrochemical workstation of CHI660EB18411A model produced by the Haihua instrument limited company, and a charging signal of a 100 mu F capacitor is collected.
3. Power density test for prepared Cu-MOF friction nano generator
The mechanical energy at 5Hz frequency was simulated with a model SUTP voice coil motor of model ten thousand up to motor manufacturing limited under room temperature environment. And two copper wires are respectively connected to two ends of an SR570 type low-noise current amplifier produced by Stanford Research System company to collect short-circuit current signals. Testing current I under load resistors with different resistance values by externally connecting 1k-1G omega, and calculating power W=I in unit area 2 R/S。
4. Lighting test of prepared Cu-MOF friction nano generator on LED lamp
The mechanical energy at 5Hz frequency was simulated with a model SUTP voice coil motor of model ten thousand up to motor manufacturing limited under room temperature environment. And then the two copper wires are respectively connected to a rectifier to integrate the alternating current into direct current. And finally, connecting wires on the rectifier to 500 LED lamp panels respectively, and performing a lighting test on the LED lamps.
5. Stability test of prepared Cu-MOF friction nano generator
The Cu-MOF in the embodiment 2 is recovered and reused as a friction power generation material to prepare the friction nano power generator, and the change condition of the current is monitored under the long-time working state, and the specific method is the same as above.
While the basic principles, principal features and advantages of the present invention have been described in the foregoing examples, it will be appreciated by those skilled in the art that the present invention is not limited by the foregoing examples, but is merely illustrative of the principles of the invention, and various changes and modifications can be made without departing from the scope of the invention, which is defined by the appended claims.
Claims (8)
1. A friction nano power generation material based on Cu-MOF is characterized in that: the friction nano power generation material is a crystalline MOF material, and the molecular structure is { [ CuC ] 21 H 18 N 6 O 9 } n Wherein n= infinity; the friction nano power generation material is monoclinic system and space groupP2 1 /n，The unit cell parameters are a= 10.3397 (6) a, b= 14.6943 (8) a, c= 14.9974 (8) a, α=90, β= 90.685 (2), γ=90, the smallest structural unit of which consists of 1 copper ion, 0.5 1,1' - [1, 4-phenylene bis (methylene)]Bis (3, 5-dicarboxypyridine) and 1 azopyridine molecule.
2. The method for synthesizing the Cu-MOF-based friction nano power generation material according to claim 1, characterized by comprising the steps of: the method comprises the steps of sealing a mixture of copper nitrate trihydrate, 1' - [1, 4-phenylene bis (methylene) ] bis (3, 5-dicarboxypyridine), azo bis (2-pyridine), N-dimethylformamide and water in a glass bottle, sufficiently oscillating in an ultrasonic cleaner until the mixture is completely dissolved, then placing the mixture in an oven for hydrothermal reaction, cooling to room temperature after the reaction is finished to obtain green blocky crystals, washing the green blocky crystals with mother liquor, and drying the green blocky crystals to obtain the friction nano power generation material based on Cu-MOF.
3. The method for synthesizing the Cu-MOF based friction nano power generation material according to claim 2, wherein: the molar ratio of copper nitrate trihydrate, 1' - [1, 4-phenylenedi (methylene) ] bis (3, 5-dicarboxypyridine) and azobis (2-pyridine) is 10:2:5.
4. The method for synthesizing the Cu-MOF based friction nano power generation material according to claim 2, wherein: the volume ratio of the N, N-dimethylformamide to the water is 1:1.
5. The method for synthesizing the Cu-MOF based friction nano power generation material according to claim 2, wherein: the temperature of the hydrothermal reaction is 90 ℃, and the time of the hydrothermal reaction is 24 hours.
6. The method for synthesizing the Cu-MOF based friction nano power generation material according to claim 2, wherein: the cooling rate when cooling to room temperature is 10 ℃/h.
7. The use of a Cu-MOF based friction nano power generation material as set forth in claim 1 in a vertical contact separation friction nano power generator characterized in that: the friction nano power generation material based on Cu-MOF is used for constructing the friction nano power generator Cu-MOF-TENG.
8. The use according to claim 7, characterized in that: when copper sheets and Kapton films are used as the conducting layer and the charge storage layer respectively, and the friction nano power generation material based on Cu-MOF and polyvinylidene fluoride are used as the friction layer, the charge density and the power density can reach 135.64 mu C.m -2 And 9841.50 mW.m -2 。
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