CN114957699B - Cu-MOF-based triboelectric nanomaterials and their preparation methods and applications - Google Patents

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

Cu-MOF-based triboelectric nanomaterials and their preparation methods and applications

technical field

The invention belongs to the technical field of triboelectric power generation materials, and in particular relates to a Cu-MOF-based triboelectric nanometer power generation material and its preparation method and application.

Background technique

With the excessive use of fossil energy, people are facing a huge energy crisis. There are also many problems in the development of many renewable energy sources. For example, the process of collecting solar energy, wave energy, and wind energy will be affected by the environment and weather, and the efficiency of energy conversion is very low. Triboelectric nanogenerator (TENG) can fully convert the neglected energy in the environment into electrical energy through the coupling effect of triboelectric electrification and electrostatic induction. Due to their small size and easy fabrication, triboelectric nanogenerators are very suitable for powering electronic devices. However, currently reported triboelectric materials are difficult to meet the demands of self-powered sensors with high stability, high efficiency, and versatility. Therefore, it is of great significance to design and develop triboelectric materials with excellent output performance and cycle stability. Metal-organic frameworks (MOFs) materials have been found to have triboelectric nanogenerator output properties and play important practical applications in energy storage, catalysis, and corrosion protection. Compared with polymer insulating electrolyte materials such as poly(tetrafluoroethylene), MOFs have functional frameworks and open channels, which can lead to higher output performance and complex functional diversity. Therefore, it is of great practical significance to synthesize new metal-organic framework materials and develop them into triboelectric materials with high performance, low cost, good reproducibility and durability.

Contents of the invention

Aiming at the problems existing in the prior art, the present invention provides a method for preparing a crystalline MOF material with high performance and strong stability applied to vertical contact-separation triboelectric power generation. The present invention utilizes 1,1'-[1,4-phenylene bis(methylene)]bis(3,5-dicarboxypyridine) and azobis(2-pyridine) as organic ligands. At the same time, this material is also used as the electrode material of the vertical contact separation triboelectric nanogenerator.

In order to solve the problems of the technologies described above, the present invention adopts the following technical solutions:

A Cu-MOF-based triboelectric nanometer power generation material is a crystalline MOF material with a molecular structure of {[CuC ₂₁ H ₁₈ N ₆ O ₉ } _n , where n=∞.

α＝90，β＝90.685(2)，γ＝90，其最小结构单元由1个铜离子，0.5个1,1'-[1,4-亚苯基双(亚甲基)]双(3,5-二羧基吡啶)和1个偶氮吡啶分子组成。The triboelectric nano-power generation material is a monoclinic crystal system with space group P2 ₁ /n, and the unit cell parameter is

α=90, β=90.685(2), γ=90, its smallest structural unit consists of 1 copper ion, 0.5 1,1'-[1,4-phenylene bis(methylene)]bis(3 , 5-dicarboxypyridine) and 1 azopyridine molecule.

The synthesis method of the Cu-MOF-based triboelectric nano power generation material of the present invention comprises the following steps:

(1) Copper nitrate trihydrate, 1,1'-[1,4-phenylenebis(methylene)]bis(3,5-dicarboxypyridine), azobis(2-pyridine), N , the mixture of N-dimethylformamide and water is sealed in a glass bottle, and fully shaken in an ultrasonic cleaner for five minutes until it is completely dissolved;

(2) placed in a 90°C oven for 24 hours;

(3) Cool down to room temperature at a rate of 10 °C/h to obtain green blocky crystals, wash with mother liquor, and dry to obtain Cu-MOF, a triboelectric nano-power generation material based on Cu-MOF.

Further, in the step (1), copper nitrate trihydrate, 1,1'-[1,4-phenylenebis(methylene)]bis(3,5-dicarboxypyridine) and azobis(2 -pyridine) in a mol ratio of 10:2:5, and in N,N-dimethylformamide and water in a volume ratio of 1:1.

Application of the Cu-MOF-based triboelectric nanopower generation material in the vertical contact separation triboelectric nanogenerator according to the present invention: Cu-MOF is used to construct the triboelectric nanogenerator Cu-MOF-TENG. And with the polyvinylidene fluoride material as the counter electrode, the current, charge density, electric power density, charging of the capacitor and the lighting of the LED lamp were tested and tested on Cu-MOF-TENG. The results show that Cu-MOF can be used as a friction Nano power generation materials, effective use of mechanical energy.

The present invention uses a copper sheet and a Kapton film as a conductive layer and a charge storage layer respectively, and a crystal powder material (triboelectric nanometer power generation material based on Cu-MOF) and polyvinylidene fluoride as a friction layer. The Cu-MOF-TENG electrode material of the present invention not only has excellent performance, but also has good stability. Under vertical contact separation mode and 5Hz working conditions, the charge density and power density can reach 135.64μC·m ^-2 and 9841.50mW m ^-2 . The short-circuit current reaches 109.32μA and can maintain a stable output state within 10000s, laying the foundation for commercial applications. Meanwhile, the Cu-MOF-TENG can light up 500 commercial LED lights under the condition of 5Hz operation.

Compared with the prior art, the present invention has the following beneficial effects:

1. The Cu-MOF of the present invention is prepared by a common hydrothermal process. The preparation method is simple and easy, and it is also easier to produce in batches and reduce costs. It provides a new choice for triboelectric nano-power generation materials, and at the same time expands the crystalline MOF The application value of the material;

2. The charge density and power density of the Cu-MOF-TENG of the present invention can reach 135.64μC·m ^-2 and 9841.50mW m ^-2 in the vertical contact separation mode and 5Hz working conditions, indicating that it has high triboelectric power generation performance , higher than that of other materials that have been reported.

3. The Cu-MOF-TENG electrode material of the present invention has good stability and can maintain a stable output state for 10,000s, laying the foundation for commercial applications.

Description of drawings

Figure 1 is the molecular formula of 1,1'-[1,4-phenylenebis(methylene)]bis(3,5-dicarboxypyridine) ligand used in material preparation.

Figure 2 is the molecular formula of the azobis(2-pyridine) ligand used in the preparation of the material.

Fig. 3 is a structural diagram of the crystal material Cu-MOF in Example 1.

Fig. 4 is an X-ray powder diffraction pattern of the crystal material Cu-MOF in Example 1.

FIG. 5 is a thermogravimetric diagram of the crystal material Cu-MOF of Example 1. FIG.

Fig. 6 is an ultraviolet diagram of Cu-MOF, the crystal material of Example 1.

Fig. 7 The short-circuit current diagram of Cu-MOF-TENG under the working condition of 5 Hz.

Figure 8. Charge density diagram of Cu-MOF-TENG under 5Hz operation.

Figure 9. Cu-MOF-TENG charging time chart of 100μF under 5Hz working condition.

Fig. 10 Cu-MOF-TENG electric power density test diagram under 5Hz working condition.

Fig. 11 Cu-MOF-TENG lighting up 500 LED lamps under the condition of 5Hz operation.

Figure 12 Cycling stability of Cu-MOF-TENG short-circuit current under 5Hz operation.

Detailed ways

The above-mentioned contents of the present invention are described in further detail below through the embodiments, but this should not be interpreted as the scope of the above-mentioned themes of the present invention being limited to the following embodiments, and all technologies realized based on the above-mentioned contents of the present invention all belong to the scope of the present invention.

Example 1

The preparation method of the Cu-MOF-based triboelectric nano-power generation material of this embodiment is as follows:

Copper nitrate hexahydrate (CuNO ₃ ·3H ₂ O) (0.0242 g, 0.1 mmol), 1,1'-[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, N-dimethyl A mixture of formamide (3ml) and H ₂ O (3ml) was sealed in a 10ml glass bottle, and was thoroughly shaken in an ultrasonic cleaner for five minutes until completely dissolved, and then placed in an oven at 90°C for 24 hours. Cool down to room temperature at a rate of 10 °C/h to obtain green blocky crystals, wash with mother liquor, and dry to obtain the target product Cu-MOF.

The crystal structure measured by single crystal X-ray diffractometer is shown in Fig. 2 .

The crystallographic parameters of Cu-MOF are detailed in the table below.

材料Cu-MOF进行X射线粉末衍射分析

X-ray powder diffraction analysis of material Cu-MOF

The crystal material Cu-MOF was crushed and placed in a mortar for 0.5h to obtain a uniform powder. The PANalytical X'Pert PRO powder single crystal diffractometer was used to obtain the powder X-ray diffraction pattern through Cu-Kα ray radiation for 5 minutes. As shown in Figure 4, the peak position of the powder X-ray diffraction pattern obtained by the test is consistent with the theoretical pattern, which shows that the Cu-MOF obtained in Example 1 has a high phase purity and can maintain a good crystalline state.

2. Thermogravimetric analysis of crystal material Cu-MOF

The dried Cu-MOF material was placed in a Netzsch STA 449C thermal analyzer, air was introduced, and thermogravimetric analysis was performed at a heating rate of 10 °C min. As shown in Figure 5, Cu-MOF can remain stable at 250°C, which shows that the Cu-MOF obtained in Example 1 has a wide temperature range.

3. UV analysis of crystal material Cu-MOF

The dried Cu-MOF material was placed in a mortar and ground for 0.5 h to obtain a uniform powder. And use Lambda-950 ultraviolet-visible spectrophotometer to test, select 250-800nm wavelength to obtain ultraviolet-visible spectrum. As shown in Figure 6, Cu-MOF has strong absorption peaks at 332nm and 668nm, which shows that the Cu-MOF obtained in Example 1 has the characteristic ultraviolet absorption peaks of typical copper coordination polymers.

Example 2

Application of the Cu-MOF-based triboelectric nanopower generation material in the vertical contact separation triboelectric nanogenerator according to the present invention: Cu-MOF is used to construct the triboelectric nanogenerator Cu-MOF-TENG. Use copper sheet and Kapton film as conductive layer and charge storage layer respectively, crystal powder material (triboelectric nano-power generation material based on Cu-MOF) and polyvinylidene fluoride as friction layer; and polyvinylidene fluoride material as counter electrode, The current, charge density, electric power density of Cu-MOF-TENG, the charging of the capacitor and the lighting of the LED lamp were tested. The results show that Cu-MOF can be used as a triboelectric nano-power generation material to effectively utilize mechanical energy.

The assembly process of Cu-MOF-TENG is as follows: Using the triboelectric nano-power generation material Cu-MOF prepared in Example 1, first coat the crushed Cu-MOF powder on a 5 cm × 5 cm copper sheet, and then apply a 5 cm × 5 cm copper sheet. A 6cm copper sheet was adhered on the counter electrode as a conductive layer, and the copper wires were respectively fixed on the copper sheet with conductive silver epoxy.

1. Conduct short-circuit current test on the prepared Cu-MOF triboelectric nanogenerator

计算得到。At room temperature, the mechanical energy of different frequencies is simulated by using the SUTP voice coil motor of Wanda Motor Manufacturing Co., Ltd. Then connect the two copper wires to the two ends of the SR570 low-noise current amplifier produced by Stanford Research System to collect the short-circuit current signal. The charge density σ per unit area is integrated by the curve of time and current under 5Hz operation

calculated.

2. The charging test of the prepared Cu-MOF triboelectric nanogenerator to the capacitor

At room temperature, the mechanical energy at a frequency of 5 Hz is simulated using a voice coil motor of the SUTP type from Wanzhida Motor Manufacturing Co., Ltd. Then connect the two copper wires to the rectifier to integrate the alternating current into direct current. Finally, connect the wires on the rectifier to the two ends of the CHI660EB18411A electrochemical workstation produced by Haichenhua Instrument Co., Ltd. to collect the charging signal of the 100μF capacitor.

3. Test the power density of the prepared Cu-MOF triboelectric nanogenerator

At room temperature, the mechanical energy at a frequency of 5 Hz is simulated using a voice coil motor of the SUTP type from Wanzhida Motor Manufacturing Co., Ltd. Then connect the two copper wires to the two ends of the SR570 low-noise current amplifier produced by Stanford Research System to collect the short-circuit current signal. Test the current I by externally connecting load resistors with different resistance values of 1k-1GΩ, and calculate the power per unit area W=I ² R/S.

4. The lighting test of the prepared Cu-MOF triboelectric nanogenerator on the LED lamp

At room temperature, the mechanical energy at a frequency of 5 Hz is simulated using a voice coil motor of the SUTP type from Wanzhida Motor Manufacturing Co., Ltd. Then connect the two copper wires to the rectifier to integrate the alternating current into direct current. Finally, connect the wires on the rectifier to 500 LED lamp boards respectively, and carry out the lighting test of the LED lamps.

5. Stability test of the prepared Cu-MOF triboelectric nanogenerator

The Cu-MOF in Example 2 was recovered and re-used as a triboelectric material to prepare a triboelectric nanogenerator, and the change of the current was monitored under a long-term working state, and the specific method was the same as above.

The above embodiments have described the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. What are described in the above embodiments and description are only to illustrate the principles of the present invention. Without departing from the scope of the principle of the present invention, there will be various changes and improvements in the present invention, and these changes and improvements all fall within the protection scope of the present invention.

Claims (8)

1. A Cu-MOF-based triboelectric nano power generation material, characterized in that: the triboelectric nano power generation material is a crystalline MOF material with a molecular structure of {[CuC ₂₁ H ₁₈ N ₆ O ₉ } _n , where n=∞ ; The triboelectric nano-power generation material is monoclinic, space group P 2 ₁ / n, unit cell parameters are a=10.3397(6)Å, b=14.6943(8)Å, c=14.9974(8)Å, α = 90, β=90.685(2), γ= 90, its smallest structural unit consists of 1 copper ion, 0.5 1,1'-[1,4-phenylenebis(methylene)]bis(3, 5-dicarboxypyridine) and 1 azopyridine molecule. 2. The synthesis method of Cu-MOF-based triboelectric nano-power generation material according to claim 1, characterized in that it comprises the following steps: copper nitrate trihydrate, 1,1'-[1,4-phenylene bis( Methylene)]bis(3,5-dicarboxypyridine), azobis(2-pyridine), N,N-dimethylformamide and water mixture sealed in a glass bottle, fully cleaned in an ultrasonic cleaner Vibrate until it is completely dissolved, and then place it in an oven for hydrothermal reaction. After the reaction, cool down to room temperature to obtain green blocky crystals, wash with mother liquor, and dry to obtain Cu-MOF-based triboelectric nano-power generation materials. 3. the synthesis method of the triboelectric nano power generation material based on Cu-MOF according to claim 2, is characterized in that: described copper nitrate trihydrate, 1,1'-[1,4-phenylene bis(methylene base)]bis(3,5-dicarboxypyridine) and azobis(2-pyridine) in a molar ratio of 10:2:5. 4. The synthesis method of Cu-MOF-based triboelectric nanometer power generation material according to claim 2, characterized in that: the volume ratio of the N,N-dimethylformamide and water is 1:1. 5. The method for synthesizing Cu-MOF-based triboelectric nanometer power generation materials according to claim 2, characterized in that: the temperature of the hydrothermal reaction is 90°C, and the time of the hydrothermal reaction is 24 hours. 6. The method for synthesizing Cu-MOF-based triboelectric nano-power generation materials according to claim 2, characterized in that: the cooling rate when it is lowered to room temperature is 10°C/h. 7. The application of the Cu-MOF-based triboelectric nanometer power generation material in the vertical contact separation friction nanometer generator according to claim 1, characterized in that: the Cu-MOF-based friction nanometer power generation material is used to construct the triboelectric nanometer generator Generator Cu-MOF-TENG. 8. The application according to claim 7, characterized in that: use copper sheet and Kapton film as conductive layer and charge storage layer respectively, based on Cu-MOF friction nano power generation material and polyvinylidene fluoride as friction layer The charge density and power density can reach 135.64 μC·m ^-2 and 9841.50 mW·m ^-2 .

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