A silver nanowire-intercalated zinc MOF conductive thin film and its preparation method

Abstract

The present invention belongs to the technical field of conductive thin films. Aiming at the problem of poor conductive stability of traditional conductive thin films, a silver nanowire interpenetrated zinc MOF conductive thin film and a preparation method thereof are provided. The conductive thin film is composed of silver nanowire interpenetrated zinc MOF, carbon fiber, polyurethane latex, and fluorosurfactant. The silver nanowire interpenetrated zinc MOF is prepared by a solvothermal reaction of Zn(OAc)2·6H2O, an organic ligand, and silver nanowires. The beneficial effects of the present invention are as follows: The microporous material structure of the silver nanowire interpenetrated zinc MOF forms a three-dimensional conductive network in polyurethane, which has an efficient electron transport path. The silver nanowires maintain synchronous deformation under external loads, inhibit the relative slip of the conductive network, and improve the conductive stability.

Description

Technical Field

[0001] The present invention belongs to the technical field of conductive thin films, and particularly relates to a silver nanowire interpenetrated zinc MOF conductive thin film and a preparation method thereof. Background Art

[0002] Large electronic devices such as personal computers and televisions, small electronic devices such as car navigation systems, mobile phones, and electronic dictionaries, and display devices such as OA and FA devices use liquid crystal display elements and touch screens, and these liquid crystal display elements, touch screens, solar cells and other devices all use conductive thin films.

[0003] Stretchable conductors are the basic building blocks of next-generation flexible electronic devices, and excellent electrical conductivity and stretchability are required simultaneously. However, poor interfacial adhesion between conductive fillers and polymer matrices usually causes relative sliding and misalignment of the conductive network, thereby reducing the final electrical conductivity. Many scholars have explored the application potential of this new type of stretchable conductor as a hyperthermia device and a flexible circuit connection line under complex dynamic deformations. Combining interfacial geometry with conductive stability provides a simple and effective way to prepare excellent stretchable conductors, which can be easily applied to other conductive composites and have potential applications in next-generation flexible electronic products such as flexible electronic circuits, energy harvesting and storage devices, implantable bioelectronic products, and wearable electronic devices. However, the conductive stability of traditional conductive thin films is poor, and new technologies are urgently needed to solve this problem. Summary of the Invention

[0004] (I) Technical Problems to be Solved

[0005] The purpose of the present invention is to provide a silver nanowire interpenetrated zinc MOF conductive thin film and a preparation method thereof, which solve the problem of poor conductive stability of traditional conductive thin films.

[0006] (II) Technical Solutions

[0007] To solve the above problems, the present invention provides a silver nanowire interpenetrated zinc MOF conductive thin film, which is composed of silver nanowire interpenetrated zinc MOF, carbon fiber, polyurethane latex, and fluorosurfactant. The silver nanowire interpenetrated zinc MOF is prepared by a solvothermal reaction of Zn(OAc)2·6H2O, an organic ligand, and silver nanowires.

[0008] To achieve the above object, the present invention is implemented as follows:

[0009] A preparation method of a silver nanowire interpenetrated zinc MOF conductive thin film includes the following steps:

[0010] (1) Weigh Zn(OAc)2·6H2O, 4-aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, silver nanowires, and N,N-dimethylacetamide as raw materials, and conduct a solvothermal reaction. After the reaction, cool it to room temperature at a rate of 5 °C / h, filter and wash with water to obtain a silver nanowire-intercalated zinc MOF microporous material.

[0011] (2) Weigh the silver nanowire-intercalated zinc MOF microporous material, carbon fiber, polyurethane latex, and fluorosurfactant, add them to a reactor, stir evenly to obtain a composite material, then dry it in a vacuum oven. Finally, under the condition of 10 MPa, press the composite material into a film to obtain a silver nanowire-intercalated zinc MOF conductive film.

[0012] Preferably, in the step (1), the mass ratio of Zn(OAc)2·6H2O, aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, silver nanowires, and N,N-dimethylacetamide is 3-5:2-5:2-5:4-6:5-10.

[0013] Preferably, in the step (1), the temperature of the solvothermal reaction is 90-120 °C, and the reaction time is 4-7 days.

[0014] Preferably, in the step (2), the mass ratio of the silver nanowire-intercalated zinc MOF microporous material, carbon fiber, polyurethane latex, and fluorosurfactant is 10-30:2-5:70-90:1-4.

[0015] Preferably, in the step (2), the drying temperature is 50-60 °C, the pressing temperature is 120-130 °C, and the pressing time is 8-10 minutes.

[0016] (3) Compared with the prior art, the beneficial effects of the method of the present invention are:

[0017] (1) The present invention provides a silver nanowire-intercalated zinc MOF conductive film and a preparation method thereof. The structure of the silver nanowire-intercalated zinc MOF microporous material forms a three-dimensional conductive network in polyurethane, having an efficient electron transport path. The silver nanowires maintain synchronous deformation under external loads, inhibit the relative slip of the conductive network, and improve the conductive stability.

[0018] (2) The present invention provides a silver nanowire-intercalated zinc MOF conductive film and a preparation method thereof. The silver nanowire-intercalated zinc MOF is prepared by a solvothermal reaction from Zn(OAc)2·6H2O and silver nanowires. A composite material composed of the silver nanowire-intercalated zinc MOF, carbon fiber, polyurethane latex, and fluorosurfactant is hot-pressed to form a conductive film.

[0019] (3) The present invention provides a silver nanowire interpenetrated zinc MOF conductive film and a preparation method thereof. Carbon fiber and silver nanowire interpenetrated zinc MOF are introduced into a polyurethane composite material. The microporous material structure of the silver nanowire interpenetrated zinc MOF serves as a bridge to tightly bond the carbon fiber and the polyurethane matrix, greatly improving the interfacial adhesion and inhibiting the sliding displacement of the conductive filler under external loads, which helps to obtain excellent mechanical strength and conductive stability. Specific Embodiments

[0020] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0021] Example 1

[0022] A preparation method of a silver nanowire interpenetrated zinc MOF conductive film includes the following steps:

[0023] The mass ratio is as follows: the mass ratio of Zn(OAc)2·6H2O, 4-aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, silver nanowires, and N,N-dimethylacetamide is 3:2:2:4:5, and the mass ratio of the silver nanowire interpenetrated zinc MOF microporous material, carbon fiber, polyurethane latex, and fluorosurfactant is 10:2:70:1.

[0024] (1) Weigh Zn(OAc)2·6H2O, 4-aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, silver nanowires, and N,N-dimethylacetamide as raw materials, and carry out a solvothermal reaction. The reaction temperature is 90 °C, the reaction time is 4 days. After the reaction, it is cooled to room temperature at a rate of 5 °C / h, filtered and washed with water to obtain the silver nanowire interpenetrated zinc MOF microporous material;

[0025] (2) Weigh the silver nanowire interpenetrated zinc MOF microporous material, carbon fiber, polyurethane latex, and fluorosurfactant and add them to a reactor and stir evenly to obtain a composite material. Then it is dried in a vacuum oven at a drying temperature of 50 °C. Finally, under the condition of 10 MPa, the composite material is pressed into a film at a pressing temperature of 120 °C and a pressing time of 8 minutes to obtain the silver nanowire interpenetrated zinc MOF conductive film.

[0026] Example 2

[0027] A preparation method of a silver nanowire interpenetrated zinc MOF conductive film includes the following steps:

[0028] The mass ratio is as follows: the mass ratio of Zn(OAc)2·6H2O, aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, silver nanowires, and N,N-dimethylacetamide is 3.5:2.5:2.5:4.5:5.5, and the mass ratio of silver nanowire-intercalated zinc MOF microporous material, carbon fiber, polyurethane latex, and fluorosurfactant is 12:2.5:75:1.5.

[0029] (1) Weigh Zn(OAc)2·6H2O, 4-aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, silver nanowires, and N,N-dimethylacetamide as raw materials, and carry out a solvothermal reaction. The reaction temperature is 100 °C, and the reaction time is 5 days. After the reaction, it is cooled to room temperature at a rate of 5 °C / h, filtered and washed with water to obtain a silver nanowire-intercalated zinc MOF microporous material;

[0030] (2) Weigh the silver nanowire-intercalated zinc MOF microporous material, carbon fiber, polyurethane latex, and fluorosurfactant and add them to a reactor, stir evenly to obtain a composite material, and then dry it in a vacuum oven. The drying temperature is 52 °C. Finally, under the condition of 10 MPa, the composite material is pressed into a film. The pressing temperature is 122 °C, and the pressing time is 8.5 minutes to obtain a silver nanowire-intercalated zinc MOF conductive film.

[0031] Example 3

[0032] A preparation method of a silver nanowire-intercalated zinc MOF conductive film includes the following steps:

[0033] The mass ratio is as follows: the mass ratio of Zn(OAc)2·6H2O, aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, silver nanowires, and N,N-dimethylacetamide is 4:4:4:5:6, and the mass ratio of silver nanowire-intercalated zinc MOF microporous material, carbon fiber, polyurethane latex, and fluorosurfactant is 25:4:80:3.

[0034] (1) Weigh Zn(OAc)2·6H2O, 4-aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, silver nanowires, and N,N-dimethylacetamide as raw materials, and carry out a solvothermal reaction. The reaction temperature is 110 °C, and the reaction time is 6 days. After the reaction, it is cooled to room temperature at a rate of 5 °C / h, filtered and washed with water to obtain a silver nanowire-intercalated zinc MOF microporous material;

[0035] (2) Weigh the silver nanowire-intercalated zinc MOF microporous material, carbon fiber, polyurethane latex, and fluorosurfactant and add them to a reactor, stir evenly to obtain a composite material, and then dry it in a vacuum oven. The drying temperature is 55 °C. Finally, under the condition of 10 MPa, the composite material is pressed into a film. The pressing temperature is 125 °C, and the pressing time is 9 minutes to obtain a silver nanowire-intercalated zinc MOF conductive film.

[0036] Example 4

[0037] A preparation method of a silver nanowire interpenetrated zinc MOF conductive film includes the following steps:

[0038] The mass ratio is as follows: the mass ratio of Zn(OAc)2·6H2O, 4-aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, silver nanowires, and N,N-dimethylacetamide is 5:5:5:6:10, and the mass ratio of the silver nanowire interpenetrated zinc MOF microporous material, carbon fiber, polyurethane latex, and fluorosurfactant is 30:5:90:4.

[0039] (1) Weigh Zn(OAc)2·6H2O, 4-aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, silver nanowires, and N,N-dimethylacetamide as raw materials, and carry out a solvothermal reaction. The reaction temperature is 120 °C, the reaction time is 7 days. After the reaction is completed, it is cooled to room temperature at a rate of 5 °C / h, filtered and washed with water to obtain a silver nanowire interpenetrated zinc MOF microporous material;

[0040] (2) Weigh the silver nanowire interpenetrated zinc MOF microporous material, carbon fiber, polyurethane latex, and fluorosurfactant and add them to a reactor and stir evenly to obtain a composite material. Then it is dried in a vacuum oven at a drying temperature of 60 °C. Finally, under the condition of 10 MPa, the composite material is pressed into a film at a pressing temperature of 130 °C and a pressing time of 10 minutes to obtain a silver nanowire interpenetrated zinc MOF conductive film.

[0041] Comparative Example 1

[0042] A preparation method of a zinc MOF conductive film includes the following steps:

[0043] The mass ratio is as follows: the mass ratio of Zn(OAc)2·6H2O, 4-aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, and N,N-dimethylacetamide is 3:2:2:5, and the mass ratio of zinc MOF, carbon fiber, polyurethane latex, and fluorosurfactant is 10:2:70:1.

[0044] (1) Weigh Zn(OAc)2·6H2O, 4-aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, and N,N-dimethylacetamide as raw materials, and carry out a solvothermal reaction. The reaction temperature is 90 °C, the reaction time is 4 days. After the reaction is completed, it is cooled to room temperature at a rate of 5 °C / h, filtered and washed with water to obtain a zinc MOF microporous material;

[0045] (2) Weigh zinc MOF, carbon fiber, polyurethane latex, and fluorosurfactant, add them to a reactor, stir evenly to obtain a composite material, then dry it in a vacuum oven at a drying temperature of 50 °C. Finally, under the condition of 10 MPa, press the composite material into a film at a pressing temperature of 120 °C and a pressing time of 8 minutes to obtain a zinc MOF conductive film.

[0046] Tensile strength test method: For the specimens in Examples 1-4 and Comparative Example 1, prepare specimens with a width of 15 mm and a sampling length of not less than 150 mm, ensure a gauge length of 100 mm, test speed: 500 ± 30 mm / min, specimen clamping: Place the specimen between the two clamps of an electronic tensile testing machine, align the longitudinal axis of the specimen with the center line connecting the upper and lower clamps, and make the clamps appropriately tight.

[0047] Elongation at break test method: For the specimens in Examples 1-4 and Comparative Example 1, prepare long strip specimens with a width of 10 mm and a total length of not less than 150 mm, and a gauge length of at least 50 mm. The test results of tensile strength and elongation at break are shown in Table 1.

[0048] Table 1

[0049]

[0050] It can be seen from Table 1 that the tensile strength and elongation at break of the films in Examples 1-4 are both greater than those of the film in Comparative Example 1, indicating that the films of the present invention have good mechanical properties.

[0051] Conductivity stability test: Tie the conductive film with copper wire, use a universal tensile testing machine (Model RGL-10 manufactured by Shenzhen Leige Instrument Co., Ltd.) to perform axial tensile deformation on the sample, and use a Keithley 4200 instrument to measure the conductivity of the sample. The test results are shown in Table 2.

[0052] Table 2

[0053]

[0054] It can be seen from Table 2 that the conductivity stability of the films in Examples 1-4 is better than that of Comparative Example 1, indicating that the films of the present invention have good conductivity stability.

[0055] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and without departing from the spirit or basic characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention.

[0056] In addition, it should be understood that although this specification is described in terms of embodiments, not every embodiment contains only one independent technical solution. This narrative manner of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A silver nanowire-intercalated zinc MOF conductive thin film, characterized in that, It consists of silver nanowire-intercalated zinc MOF, carbon fiber, polyurethane latex, and fluorosurfactant. The specific preparation steps of the silver nanowire-intercalated zinc MOF conductive film are as follows: (1) Weigh Zn(OAc)2·6H2O, 4-aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, silver nanowires, and N,N-dimethylacetamide as raw materials and carry out a solvothermal reaction. After the reaction, cool it to room temperature at a rate of 5 °C / h, filter and wash with water to obtain the silver nanowire-intercalated zinc MOF microporous material. The mass ratio of Zn(OAc)2·6H2O, aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, silver nanowires, and N,N-dimethylacetamide is 3-5:2-5:2-5:4-6:5-10; (2) Weigh the silver nanowire-intercalated zinc MOF microporous material, carbon fiber, polyurethane latex, and fluorosurfactant, add them to a reactor and stir evenly to obtain a composite material. Then dry it in a vacuum oven. Finally, under the condition of 10 MPa, press the composite material into a film to obtain the silver nanowire-intercalated zinc MOF conductive film. The mass ratio of the silver nanowire-intercalated zinc MOF microporous material, carbon fiber, polyurethane latex, and fluorosurfactant is 10-30:2-5:70-90:1-4.

2. A preparation method of a silver nanowire interpenetrated zinc MOF conductive film, characterized in that, It includes the following steps: (1) Weigh Zn(OAc)2·6H2O, 4-aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, silver nanowires, and N,N-dimethylacetamide as raw materials and carry out a solvothermal reaction. After the reaction, cool it to room temperature at a rate of 5 °C / h, filter and wash with water to obtain the silver nanowire-intercalated zinc MOF microporous material; (2) Weigh the silver nanowire-intercalated zinc MOF microporous material, carbon fiber, polyurethane latex, and fluorosurfactant, add them to a reactor and stir evenly to obtain a composite material. Then dry it in a vacuum oven. Finally, under the condition of 10 MPa, press the composite material into a film to obtain the silver nanowire-intercalated zinc MOF conductive film; In the step (1), the mass ratio of Zn(OAc)2·6H2O, aminopyridine, 3,3',5,5'-terphenyltetracarboxylic acid, silver nanowires, and N,N-dimethylacetamide is 3-5:2-5:2-5:4-6:5-10; in the step (2), the mass ratio of the silver nanowire-intercalated zinc MOF, carbon fiber, polyurethane latex, and fluorosurfactant is 10-30:2-5:70-90:1-4.

3. The preparation method of a silver nanowire interpenetrated zinc MOF conductive thin film according to claim 2, characterized in that, In the step (1), the solvothermal reaction temperature is 90-120 °C and the reaction time is 4-7 days.

4. The preparation method of a silver nanowire interpenetrated zinc MOF conductive thin film according to claim 2, wherein, In the step (2), the drying temperature is 50-60 °C, the pressing temperature is 120-130 °C, and the pressing time is 8-10 minutes.

Images