阅读说明：本技术 基于锰基配合物的摩擦纳米发电材料及其制备方法和应用 (Friction nanometer power generation material based on manganese-based complex and preparation method and application thereof ) 是由 邵志超 陈军帅 胡仁堂 张展 米立伟 于 2021-09-28 设计创作，主要内容包括：本发明公开了一种基于锰基配合物的摩擦纳米发电材料及其制备方法和应用,属于摩擦发电技术领域。将氯化锰四水合物、1-(4-羧基苯基)-苯并咪唑-5-羧酸、N,N-二甲基甲酰胺、甲醇和水的混合物密封在玻璃瓶中,在超声波清洗机内充分震荡五分钟直至完全溶解；放置在90℃烘箱中反应24小时；以10℃/h的速率降至室温,得到淡黄色块状晶体,用母液洗涤,干燥,得到基于锰基配合物的摩擦纳米发电材料Mn-MOF。本发明还公开了该材料的制备方法及其在垂直接触分离式摩擦纳米发电机的应用。本发明制备的Mn-MOF-TENG稳定性较好,且在摩擦发电测试中表现出了优异的输出性能和循环稳定性,为晶态摩擦发电材料提供了新的选择,也拓展了晶态MOFs材料的合成路线和应用价值。(The invention discloses a friction nano power generation material based on a manganese-based complex, and a preparation method and application thereof, and belongs to the technical field of friction power generation. Sealing a mixture of manganese chloride tetrahydrate, 1- (4-carboxyphenyl) -benzimidazole-5-carboxylic acid, N-dimethylformamide, methanol and water in a glass bottle, and fully shaking for five minutes in an ultrasonic cleaner until the mixture is completely dissolved; placing the mixture in an oven at 90 ℃ for reaction for 24 hours; and (3) cooling to room temperature at the speed of 10 ℃/h to obtain a light yellow blocky crystal, washing with mother liquor, and drying to obtain the manganese-based complex-based friction nano power generation material Mn-MOF. The invention also discloses a preparation method of the material and application of the material in a vertical contact separation type friction nano generator. The Mn-MOF-TENG prepared by the invention has good stability, shows excellent output performance and cycle stability in a friction power generation test, provides a new choice for a crystalline friction power generation material, and also expands the synthetic route and application value of the crystalline MOFs material.)

1. A friction nanometer power generation material based on a manganese-based complex is characterized in that: the friction nanometer power generation material is a crystalline MOF material, and the molecular structure is { [ Mn { [₂(L)₂DMF] } _n Wherein n = ∞.

2. The method for synthesizing a friction nano power generation material based on a manganese-based complex according to claim 1, characterized by comprising the following steps:

(1) sealing a mixture of manganese chloride tetrahydrate, 1- (4-carboxyphenyl) -benzimidazole-5-carboxylic acid, N-dimethylformamide, methanol and water in a glass bottle, and fully shaking for five minutes in an ultrasonic cleaner until the mixture is completely dissolved;

(2) placing the mixture in an oven at 90 ℃ for reaction for 24 hours;

(3) and (3) cooling to room temperature at the speed of 10 ℃/h to obtain a light yellow blocky crystal, washing with mother liquor, and drying to obtain the manganese-based complex-based friction nano power generation material Mn-MOF.

3. The method for synthesizing the friction nano power generation material based on the manganese-based complex according to claim 1, wherein the method comprises the following steps: in the step (1), the molar ratio of the manganese chloride tetrahydrate to the 1- (4-carboxyphenyl) -benzimidazole-5-carboxylic acid is 4:1, and the volume ratio of the N, N-dimethylformamide to the methanol to the water is 4:2: 1.

4. Use of the manganese-based complex-based triboelectric nanomachinery material according to claim 1 in vertical contact separation-type triboelectric nanomachinery generators, characterized in that: the friction nano-electricity generation material Mn-MOF based on the manganese-based complex is used for constructing a friction nano-electricity generator Mn-MOF-TENG.

5. Use of a triboelectric nanoelectrical material based on manganese-based complexes according to claim 4, characterized in that: the preparation method of the friction nano-generator Mn-MOF-TENG comprises the following steps: a. mechanically grinding the manganese-based complex-based friction nano power generation material Mn-MOF bulk crystals by using a mortar, coating crushed crystal powder on a copper sheet of 5cm multiplied by 5cm, and fixing a copper wire on the other side of the copper sheet through silver epoxy resin to serve as an electrode material for friction power generation;

b. dissolving polyvinylidene fluoride powder in acetone and N, N-dimethylacetamide to form a polyvinylidene fluoride solution, and spin-coating the prepared polyvinylidene fluoride solution on a Kapton film;

c. and adhering a copper sheet to the other side of the Kapton film coated with the polyvinylidene fluoride, and fixing a copper wire on the copper sheet by using conductive silver epoxy resin to serve as a counter electrode for friction power generation.

6. Use of a triboelectric nanoelectrical material based on manganese-based complexes according to claim 5, characterized in that: and in the step b, spin-coating the polyvinylidene fluoride solution on the Kapton film for 90 seconds through a KW-4A desk type straightener at the speed of 3000 r/min, and drying in an oven at the temperature of 80 ℃.

7. Use of a triboelectric nanoelectrical material based on manganese-based complexes according to claim 5, characterized in that: when a copper sheet and a Kapton film are used as a conductive layer and a charge storage layer, respectively, and a crystal powder material and polyvinylidene fluoride are used as a friction layer, the charge density and the power density can reach 57.62 mu C.m^-21211.04mW m^-2。

Technical Field

The invention belongs to the technical field of friction power generation materials, and particularly relates to a friction nano power generation material based on a manganese-based complex, and a preparation method and application thereof.

Background

With the advent of the network and the artificial intelligence era, thousands of multifunctional mobile electronic devices have been in force. For example, various sensors for health monitoring, healthcare, environmental protection, infrastructure monitoring, and security will be located throughout every corner of our lives. The supply of energy to support the proper operation of these electronic devices is an important issue that needs to be addressed. The mobility of these numerous electronic devices requires distributed energy sources, which are typically provided by solar, thermal, wind, and mechanical vibrations, where the collection of solar and thermal energy can be limited by various specific circumstances. While a friction nano-generator (TENG) that can directly convert mechanical energy such as wind current, sea waves and human body movement into electrical energy would be a very suitable energy supply device. The friction nano generator converts mechanical energy into electric energy by utilizing the coupling effect of contact electrification and electrostatic induction. However, the currently reported friction power generation materials have difficulty in satisfying the demands of a self-powered sensor of high stability, high efficiency, and versatility. The design and development of the triboelectric material with excellent output performance and cycling stability have very important significance.

Metal organic framework materials have begun to be applied in the field of triboelectric power generation due to the adjustability and functional designability of the structure. Generally, the organic ligand with a large conjugated structure is considered as a new ideal friction nano power generation material. Compared with the traditional friction power generation material, the crystalline MOF material has high aperture ratio and regular pore channels, the cavity can be modified and functionalized, and the crystalline MOF material has narrow gap bands, and the precise structure measurement can provide the structure-activity relationship between the platform research performance and the friction power generation performance, so that the crystalline MOF material has wide development prospect in developing the high-efficiency friction nano power generation material.

Disclosure of Invention

The invention solves the technical problem of providing a crystal with high performance and strong stability for vertical contact separation type friction power generationMethods of making a phase MOF material. The invention utilizes 1- (4-carboxyphenyl) -benzimidazole-5-carboxylic acid (L) as an organic ligand to construct a novel crystalline MOF material { [ Mn ] with excellent friction power generation performance through self-assembly with manganese ions₂(L)₂DMF] } _n (Mn-MOF). Meanwhile, the material is also used as an electrode material of a vertical contact separation type friction nano generator.

In order to solve the technical problems, the invention adopts the following technical scheme:

the friction nano power generation material based on the manganese-based complex is a crystalline MOF material, and the molecular structure of the material is { [ Mn ]₂(L)₂DMF] } _n Wherein n = ∞.

The invention relates to a method for synthesizing a friction nano power generation material based on a manganese-based complex, which comprises the following steps of:

(1) sealing a mixture of manganese chloride tetrahydrate, 1- (4-carboxyphenyl) -benzimidazole-5-carboxylic acid, N-dimethylformamide, methanol and water in a glass bottle, and fully shaking for five minutes in an ultrasonic cleaner until the mixture is completely dissolved;

(2) placing the mixture in an oven at 90 ℃ for reaction for 24 hours;

(3) and (3) cooling to room temperature at the speed of 10 ℃/h to obtain a light yellow blocky crystal, washing with mother liquor, and drying to obtain the manganese-based complex-based friction nano power generation material Mn-MOF.

Further, in the step (1), the molar ratio of the manganese chloride tetrahydrate to the 1- (4-carboxyphenyl) -benzimidazole-5-carboxylic acid is 4:1, and the volume ratio of the N, N-dimethylformamide to the methanol to the water is 4:2: 1.

The invention relates to application of a friction nanometer power generation material based on a manganese-based complex in a vertical contact separation type friction nanometer generator, which comprises the following steps: the friction nano-electricity generation material Mn-MOF based on the manganese-based complex is used for constructing a friction nano-electricity generator Mn-MOF-TENG.

The preparation method of the friction nano-generator Mn-MOF-TENG comprises the following steps: a. mechanically grinding the manganese-based complex-based friction nano power generation material Mn-MOF bulk crystals by using a mortar, coating crushed crystal powder on a copper sheet of 5cm multiplied by 5cm, and fixing a copper wire on the other side of the copper sheet through silver epoxy resin to serve as an electrode material for friction power generation;

b. dissolving polyvinylidene fluoride powder in acetone and N, N-dimethylacetamide to form a polyvinylidene fluoride solution, and spin-coating the prepared polyvinylidene fluoride solution on a Kapton film;

d. and adhering a copper sheet to the other side of the Kapton film coated with the polyvinylidene fluoride, and fixing a copper wire on the copper sheet by using conductive silver epoxy resin to serve as a counter electrode for friction power generation.

Further, in the step b, the polyvinylidene fluoride solution is spin-coated on the Kapton film for 90 seconds through a KW-4A bench leveler at the speed of 3000 rpm, and the Kapton film is placed in an oven at 80 ℃ for drying.

The polyvinylidene fluoride material is used as a counter electrode, and a test experiment is carried out on the current, voltage and electric power density of Mn-MOF-TENG, the charging condition of a capacitor and the lighting condition of an LED lamp, and the result shows that Mn-MOF can be used as a friction nano power generation material to effectively utilize mechanical energy.

The invention uses copper sheet and Kapton film as conducting layer and charge storage layer, respectively, and crystal powder material and polyvinylidene fluoride as friction layer. The Mn-MOF-TENG electrode material disclosed by the invention is excellent in performance and good in stability. Under the vertical contact separation mode and the 5Hz working condition, the charge density and the power density can reach 57.62 mu C.m^-21211.04mW m^-2. The short-circuit current and the open-circuit voltage reach 40.98 muA and 288.97V respectively, and the stable output state can be kept in 100000 cycles, which lays the foundation for commercial application. Meanwhile, Mn-MOF-TENG could light 1550 commercial LED lamps under 8hz operating conditions.

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

1. the Mn-MOF is prepared by a common hydrothermal method, the preparation method is simple and easy to implement, batch production is easier, the cost is reduced, a new choice is provided for a friction nanometer power generation material, and the application value of a crystalline MOF material is expanded;

2. the charge density and the power density of the Mn-MOF-TENG can reach 57.62 mu C.m under the vertical contact separation mode and the working condition of 5Hz^-21211.04mW m^-2Thus showing high friction power generation performance.

3. The Mn-MOF-TENG electrode material has good stability, can keep a stable output state in 100000 cycles, and lays a foundation for commercial application.

Drawings

FIG. 1 shows the molecular formula of 1- (4-carboxyphenyl) -benzimidazole-5-carboxylic acid ligand used in the preparation of materials.

FIG. 2 is a structural diagram of a crystalline material Mn-MOF.

FIG. 3 is a thermogram of the crystalline material Mn-MOF.

FIG. 4 Mn-MOF-TENG electrode material (left) and counter electrode material (right).

FIG. 5 is a graph of Mn-MOF-TENG short circuit current at 5Hz operation.

FIG. 6 is a graph comparing Mn-MOF-TENG short circuit current plots for different frequency operation.

FIG. 7 is a graph of Mn-MOF-TENG open circuit voltage at 5Hz operation.

FIG. 8 is a graph of Mn-MOF-TENG open circuit voltage vs. operating at different frequencies.

FIG. 9 is a graph of Mn-MOF-TENG charging 100 μ F at 5 Hz.

FIG. 10 is a graph of Mn-MOF-TENG charging and discharging cycles at 100 μ F at 5 Hz.

FIG. 11 is a graph of Mn-MOF-TENG electrical power density measurements at 5Hz operation.

FIG. 12 is a graph of Mn-MOF-TENG lighting 1550 LED lamps at 8Hz operation.

FIG. 13 Mn-MOF-TENG short circuit current cycling stability at 5Hz operating conditions.

FIG. 14 Mn-MOF-TENG open circuit voltage cycling stability at 5Hz operating conditions.

Detailed Description

The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.

Example 1

The preparation method of the Mn-MOF material of the embodiment is as follows:

manganese chloride tetrahydrate (MnCl)₂·4H₂O) (0.0300 g, 0.152 mmol), 1- (4-carboxyphenyl) -benzimidazole-5-carboxylic acid (C)₁₄H₁₂N₂O₄) (0.0100 g, 0.037 mmol), N-dimethylformamide (2 ml), methanol (1 ml) and H₂The mixture of O (0.5 ml) was sealed in a 10 ml glass bottle and shaken well in an ultrasonic cleaner for five minutes until completely dissolved, and then placed in an oven at 90 ℃ for reaction for 24 hours. Cooling to room temperature at the speed of 10 ℃/h to obtain light yellow blocky crystals, washing with mother liquor, drying to obtain a target product Mn complex, weighing, and obtaining the yield: 72% (based on C)₁₄H₁₂N₂O₄Calculated).

The crystal structure is shown on the left of figure 2 measured by a single crystal X-ray diffractometer.

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

。

Example 2

The Mn-MOF material prepared in example 1 was used to prepare a triboelectric nanogenerator, with the following steps:

a. mechanically grinding the manganese-based complex-based friction nano power generation material Mn-MOF bulk crystals by using a mortar, coating crushed crystal powder on a copper sheet of 5cm multiplied by 5cm, and fixing a copper wire on the other side of the copper sheet through silver epoxy resin to serve as an electrode material for friction power generation; as in fig. 4, left;

b. dissolving polyvinylidene fluoride powder in acetone and N, N-dimethylacetamide to form a polyvinylidene fluoride solution, spin-coating the prepared polyvinylidene fluoride solution on a Kapton film for 90 seconds at the speed of 3000 revolutions per minute through a KW-4A desk type straightener, and drying the film in an oven at the temperature of 80 ℃;

c. and adhering a copper sheet to the other side of the Kapton film coated with the polyvinylidene fluoride, and fixing a copper wire on the copper sheet by using conductive silver epoxy resin to serve as a counter electrode for friction power generation.

1. Short-circuit current test of prepared Mn-MOF friction nano-generator

Firstly, coating crushed Mn-MOF powder on a copper sheet with the thickness of 5cm multiplied by 5cm, then adhering a copper sheet with the thickness of 5cm multiplied by 6cm on a counter electrode to be used as a conductive layer, and fixing copper wires on the copper sheet respectively by conductive silver epoxy resin. Mechanical energy of different frequencies was simulated in a room temperature environment using a voice coil motor of the SUTP model of ten thousand to motor manufacturing ltd. Two copper wires were connected to both ends of a SR570 type low noise current amplifier manufactured by Stanford Research systems, respectively, and short circuit current signals were collected. The charge density σ per unit area is integrated from the time-current curve at 5Hz operation (σ =)) And (4) calculating.

2. Open circuit voltage test of prepared Mn-MOF friction nano-generator

Firstly, coating crushed Mn-MOF powder on a copper sheet with the thickness of 5cm multiplied by 5cm, then adhering a copper sheet with the thickness of 5cm multiplied by 6cm on a counter electrode to be used as a conductive layer, and fixing copper wires on the copper sheet respectively by conductive silver epoxy resin. Mechanical energy of different frequencies was simulated in a room temperature environment using a voice coil motor of the SUTP model of ten thousand to motor manufacturing ltd. And then two copper wires are respectively connected to two ends of a 2657A type high-power digital source meter produced by Tektronix company to collect open-circuit voltage signals.

3. Charge test of prepared Mn-MOF friction nano-generator on capacitor

Firstly, coating crushed Mn-MOF powder on a copper sheet with the thickness of 5cm multiplied by 5cm, then adhering a copper sheet with the thickness of 5cm multiplied by 6cm on a counter electrode to be used as a conductive layer, and fixing copper wires on the copper sheet respectively by conductive silver epoxy resin. Mechanical energy at a frequency of 5Hz was simulated in a room temperature environment using a voice coil motor of the type SUTP from ten thousand to motor manufacturing ltd. And then two copper wires are respectively connected to a rectifier to integrate the alternating current into the direct current. Finally, the leads on the rectifier are respectively connected to two ends of an electrochemical workstation of model CHI660E B18411A manufactured by Chenghua instruments, Inc., and charging signals of a 100 mu F capacitor are acquired.

4. Power density test of prepared Mn-MOF friction nano generator

Firstly, coating crushed Mn-MOF powder on a copper sheet with the thickness of 5cm multiplied by 5cm, then adhering a copper sheet with the thickness of 5cm multiplied by 6cm on a counter electrode to be used as a conductive layer, and fixing copper wires on the copper sheet respectively by conductive silver epoxy resin. Mechanical energy at a frequency of 5Hz was simulated in a room temperature environment using a voice coil motor of the type SUTP from ten thousand to motor manufacturing ltd. Two copper wires were connected to both ends of a SR570 type low noise current amplifier manufactured by Stanford Research systems, respectively, and short circuit current signals were collected. Testing current under load resistors externally connected with 1k-1G omega with different resistance valuesIAnd calculating the power per unit area W =I ²R/S。

5. Lighting test of prepared Mn-MOF friction nano-generator on LED lamp

Firstly, coating crushed Mn-MOF powder on a copper sheet with the thickness of 5cm multiplied by 5cm, then adhering a copper sheet with the thickness of 5cm multiplied by 6cm on a counter electrode to be used as a conductive layer, and fixing copper wires on the copper sheet respectively by conductive silver epoxy resin. Mechanical energy at a frequency of 5Hz was simulated in a room temperature environment using a voice coil motor of the type SUTP from ten thousand to motor manufacturing ltd. And then two copper wires are respectively connected to a rectifier to integrate the alternating current into the direct current. And finally, connecting the wires on the rectifier to 1550 LED lamp panels respectively to carry out lighting test on the LED lamps.

6. Friction power generation by recycling Mn-MOF material

The Mn-MOF in the example 3 is recovered and is used as a friction power generation material to prepare a friction nano-generator, and the change conditions of current and voltage are monitored under a long-time working state, and the specific method is the same as the above.

The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.