Visual conductor wire and preparation method and application thereof

Abstract

The invention provides a visual conductor wire and a preparation method and application thereof, and belongs to the technical field of conductor wire preparation. The preparation method provided by the invention comprises the following steps: uniformly mixing a perovskite solution with a first polymer solution to obtain a perovskite polymer composite spinning solution; dissolving a conductive material and a second polymer in a solvent to obtain a uniform composite conductive spinning solution; and then, through combination of a wet spinning method and an impregnation method, the perovskite polymer composite spinning solution is firstly extruded into a coagulating bath for preliminary curing and fiber forming, then the perovskite polymer composite spinning solution is immediately immersed into the composite conductive spinning solution, and finally heat treatment is performed to obtain the visual conductive wire with the skin-core structure. Fluorescence emitted by the core layer of the visual conductive wire under ultraviolet irradiation can penetrate through the skin layer, the fluorescence color and resistance are adjustable, the fluorescence intensity is high, the uniformity and the stability are good, the electronic temperature resistance of the conductive layer is good, the storage stability is good, and the application prospect is wide. The method can be used in the fields of flexible pattern display, encryption anti-counterfeiting, preparation of visual sensors and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of conductive wire preparation, and in particular to a flexible visualized conductive wire and a preparation method and application thereof. Background Art

[0002] Photoluminescent fiber refers to a new type of functional fiber that produces visible light when the luminescent center undergoes electron transition under light excitation. It can be divided into intrinsic photoluminescent fiber and universal photoluminescent fiber. Among them, intrinsic photoluminescent fiber uses the refraction mechanism of sunlight to design and regulate the fiber surface structure. Universal photoluminescent fiber is prepared by doping and modifying photoluminescent materials combined with traditional spinning methods.

[0003] With the rapid development of the Internet of Things and wearable electronic products, people have higher and higher requirements for smart wearable sensors, especially a conductive wire with high sensing performance, good durability, flexibility, and visualization characteristics, to meet the current needs of smart wearable electronic products. Therefore, it is of great significance to combine the functions of photoluminescent fibers with those of conductive fibers to prepare visualized conductive wires. However, in the prior art, the manufacturing method of visualized conductive wires is relatively complicated and expensive.

[0004] In view of this, it is necessary to develop a visualized conductive wire and a preparation method and application thereof to solve the above problems. Summary of the invention

[0005] In view of the technical problems existing in the background technology, the present application provides a visual conductive wire and a preparation method and application thereof, which combines the wet spinning method with the impregnation method, and utilizes the luminescent properties of the perovskite material and the characteristic that the fluorescence emitted by the material can penetrate the conductive layer covering its surface to prepare a visual conductive wire with a skin-core structure. The fluorescent color of the visual conductive wire is regulated by adjusting the raw material ratio and type of the perovskite, and the resistance of the visual conductive wire is regulated by adjusting the proportion of the conductive material in the cortex.

[0006] The visualized conductive wires prepared in the present application have excellent luminous brightness and wide color gamut. The fluorescent colors include blue, green, red, and yellow. The preparation cost is low and the process is simple. It can be used in the fields of flexible pattern display, encryption and anti-counterfeiting, and preparation of visualized sensors, and has good application prospects.

[0007] In a first aspect, an embodiment of the present application provides a method for preparing a visualized conductive line, comprising the following steps:

[0008] S1, uniformly mixing the perovskite solution and the first polymer solution to obtain a perovskite polymer composite spinning solution;

[0009] S2, dissolving the conductive material and the second polymer in a solvent to obtain a uniform composite conductive spinning solution;

[0010] S3, using a wet spinning method, extruding the perovskite polymer composite spinning solution obtained in step S1 into a coagulation bath to preliminarily solidify it into fibers to obtain a core layer, and quickly immersing the core layer in the composite conductive spinning solution obtained in step S2 before it is completely solidified and dried, so that the outside of the core layer is fully and evenly covered with a conductive layer to obtain a composite fiber filament, and then performing a heat treatment to dry and solidify the composite fiber filament and further crystallize the core layer material, and after natural cooling, a visual conductive line with a skin-core structure is obtained.

[0011] Further, in the perovskite solution described in step S1, the concentration of perovskite is 0.005-4.0mmol / mL, and the perovskite is AX and PbX 2 A mixture of AX and PbX 2 The molar ratio of is 1:(0.5-2), A is a mixture of one or more of cesium, methylamine, and ethylamine, and X is a mixture of one or more of I, Cl, and Br; the solvent of the perovskite solution is a mixture of one or more of N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and γ-butyrolactone (GBL).

[0012] Furthermore, in the first polymer solution described in step S1, the first polymer is polyurethane (PU), polyacrylonitrile (PAN) or polyvinyl chloride (PVC), and the concentration of the first polymer is 5-50wt%; the solvent of the first polymer solution is a mixture of one or more of DMF, DMSO, NMP, and GBL; in step S1, the volume ratio of the perovskite solution to the first polymer solution is 1:(1-30).

[0013] Furthermore, in step S2, the conductive material is a mixture of one or more carbon-based conductive materials, organic conductive materials, and metal materials, the second polymer is sodium polyacrylate (PAAS), polyethylene glycol (PEG), polymethyl methacrylate (PMMA) or polydimethylsiloxane (PDMS), and the solvent is water, ethanol, isopropanol, ethyl acetate, DMF, DMSO, toluene or chlorobenzene; wherein the concentration of the conductive material in the composite conductive spinning solution is 0.1-20wt%, and the concentration of the second polymer in the composite conductive spinning solution is 0.01-5wt%; in the composite conductive spinning solution, the hydrophilicity / hydrophobicity of the second polymer is consistent with the hydrophilicity / hydrophobicity of the conductive material and the hydrophilicity / hydrophobicity of the solvent.

[0014] Furthermore, the carbon-based conductive material is a mixture of one or more of carbon nanotubes (CNTs), carbon black (CB), graphene, and MXene; the organic conductive material is a mixture of one or more of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylethene] (MEH-PPV), poly(3-hexylthiophene), and polytriarylamine; and the metal material is a mixture of one or more of silver nanowires (AgNW), silver nanoparticles, and gold nanorods.

[0015] Furthermore, in step S3, the coagulation bath is water at room temperature, and the temperature of the heat treatment is lower than or equal to 180°C.

[0016] In the second aspect, an embodiment of the present application provides a visualized conductive wire, which is prepared according to the preparation method described in any one of the aforementioned schemes, and the visualized conductive wire is a skin-core structure. Among them, the core layer is a composite fluorescent elastic material, and the skin layer is a composite conductive material. The visualized conductive wire has a photoluminescent property, and the fluorescence emitted by the core layer under ultraviolet light penetrates the skin structure, making the fluorescence of the visualized conductive wire visible.

[0017] Furthermore, the photoluminescence color of the visualized conductive thread is regulated by changing the type and proportion of the X element contained in the core layer; when the visualized conductive thread is stored in air with constant temperature and humidity for 30 days, the decrease rate of the photoluminescence fluorescence intensity is less than 5%.

[0018] Furthermore, the resistance of the visualized conductive wire is regulated by changing the proportion of conductive material in the cortex, and the resistance regulation range is between 100Ω-1MΩ; the visualized conductive wire is stored in air with constant temperature and humidity for 24 days, and the normalized resistance change rate is less than 10%; when the storage temperature is increased from 15°C to 45°C, the normalized resistance change rate of the visualized conductive wire is less than 10%.

[0019] In a third aspect, an embodiment of the present application provides a visualized conductive wire produced by the preparation method described in any one of the aforementioned schemes or an application of the visualized conductive wire described in any one of the aforementioned schemes, wherein the visualized conductive wire is used in the fields of flexible pattern display, encryption and anti-counterfeiting, and visualization sensor preparation.

[0020] The beneficial effects of this application are as follows:

[0021] The present application provides a visualized conductive wire and a preparation method and application thereof, combining a wet spinning method with an impregnation method, utilizing the luminescent properties of perovskite materials and the characteristic that the fluorescence emitted by the material can penetrate the conductive layer covering its surface to prepare a visualized conductive wire with a skin-core structure.

[0022] (1) The preparation method of the present application has low cost, simple process, and is easy to scale up for production. The fluorescent color of the visualized conductive line can be regulated by adjusting the raw material ratio and type of the perovskite, and the resistance of the visualized conductive line can be regulated by adjusting the proportion of the conductive material in the cortex.

[0023] (2) The visualized conductive wire prepared by the present application has excellent luminous brightness and wide color gamut, and the fluorescent color is rich and adjustable, including blue, green, red, and yellow. The fluorescence of the visualized conductive wire can penetrate the cortex, so that the conductive wire presents clear and bright fluorescence, realizes visual display, and has high fluorescence intensity, good uniformity and stability. When the visualized conductive wire is placed in air with constant temperature and humidity and stored for 30 days, the fluorescence intensity and fluorescence uniformity of the photoluminescence remain basically unchanged, and the decrease rate of fluorescence intensity is less than 5%.

[0024] (3) The visualized conductive wire prepared by the present application has a wide resistance control range of 100Ω-1MΩ, and the electronic temperature resistance of the conductive layer is good and the storage stability is good. When stored in air with constant temperature and humidity for 24 days, the normalized resistance change rate is less than 10%. When the storage temperature is increased from 15°C to 45°C, the normalized resistance change rate of the visualized conductive wire is less than 10%.

[0025] (4) The visualized conductive wires prepared in the present application can be used in the fields of flexible pattern display, encryption and anti-counterfeiting, and preparation of visualized sensors, and have good application prospects.

[0026] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the technical solution of the present application, the following is a brief introduction to the drawings used in the present application. Obviously, the drawings described below are only some embodiments of the present application, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0028] Figure 1 This is a product picture of the visualized conductive wire prepared in Example 1 of the present application, wherein: Figure 1 (a) is a product picture under natural light. Figure 1 (b) is a picture of the product under ultraviolet light;

[0029] Figure 2This is a resistance change graph of the visualized conductive wire prepared in Example 1 of the present application after being stored in air at a temperature of 15° C. and a relative humidity of 69% for 24 days;

[0030] Figure 3 A resistance change diagram of the visualized conductive wire prepared in Example 1 of the present application when the ambient temperature is increased from 15° C. to 45° C. in air with a relative humidity of 69%;

[0031] Figure 4 The photoluminescence performance comparison diagram of the visualized conductive wires prepared in Examples 1-3 of the present application stored in air at a temperature of 15°C and a relative humidity of 69% for 0 days and 30 days, respectively, from left to right are Example 1 (green), Example 2 (blue), and Example 3 (red). Among them, Figure 4 (a) Figure 4 (c) Figure 4 (e) Fluorescence microscopy image of the visualized conductive wire after 0 day of storage in air; Figure 4 (b) Figure 4 (d) Figure 4 (f) Fluorescence microscopy image of the visualized conductive wire after being stored in air for 30 days;

[0032] Figure 5 This is a diagram showing the application of the visualized conductive thread in the field of flexible pattern display and anti-counterfeiting according to Application Example 1 of the present application;

[0033] Figure 6 This is a product picture of the visualized conductive wire prepared in Example 4 of the present application, wherein: Figure 6 (a) is a product picture under natural light. Figure 6 (b) is a picture of the product under ultraviolet light. DETAILED DESCRIPTION

[0034] The following embodiments of the technical solution of the present application are described in detail in conjunction with the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application, and are therefore only used as examples, and cannot be used to limit the scope of protection of the present application.

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" in the specification and claims of this application and the above-mentioned figure descriptions and any variations thereof are intended to cover non-exclusive inclusions.

[0036] In the description of the embodiments of the present application, the technical terms "first", "second", etc. are only used to distinguish different objects, and cannot be understood as indicating or implying relative importance or implicitly indicating the number, specific order or primary and secondary relationship of the indicated technical features. In the description of the embodiments of the present application, the meaning of "multiple" is more than two, unless otherwise clearly and specifically defined.

[0037] Reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0038] In the description of the embodiments of the present application, the term "and / or" is only a description of the association relationship of the associated objects, indicating that there may be three relationships. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.

[0039] In the description of the embodiments of the present application, the term "multiple" refers to more than two (including two). Similarly, "multiple groups" refers to more than two groups (including two groups), and "multiple" refers to more than two (including two).

[0040] With the rapid development of the Internet of Things and wearable electronic products, people have higher and higher requirements for smart wearable sensors, especially a conductive wire with high sensing performance, good durability, flexibility, and visualization characteristics, to meet the current needs of smart wearable electronic products. Therefore, it is of great significance to combine the functions of photoluminescent fibers with those of conductive fibers to prepare visualized conductive wires. However, in the prior art, the manufacturing method of visualized conductive wires is relatively complicated and expensive.

[0041] In order to solve the technical problem that the manufacturing method of visual conductive wire is relatively complicated and expensive, the present application provides a visual conductive wire and its preparation method and application, which combines the wet spinning method with the impregnation method, and utilizes the luminescent properties of the perovskite material and the characteristic that the fluorescence emitted by the material can penetrate the conductive layer covering its surface to prepare a visual conductive wire with a skin-core structure, and realizes the regulation of the fluorescent color of the visual conductive wire by adjusting the raw material ratio and type of the perovskite, and realizes the regulation of the resistance of the visual conductive wire by adjusting the proportion of the conductive material in the cortex.

[0042] The visualized conductive wires prepared in the present application have excellent luminous brightness and wide color gamut. The fluorescent colors include blue, green, red, and yellow. The preparation cost is low and the process is simple. It can be used in the fields of flexible pattern display, encryption and anti-counterfeiting, and preparation of visualized sensors, and has good application prospects.

[0043] In a first aspect, an embodiment of the present application provides a method for preparing a visualized conductive line, comprising the following steps:

[0044] S1, uniformly mixing the perovskite solution and the first polymer solution to obtain a perovskite polymer composite spinning solution.

[0045] In some embodiments, the volume ratio of the perovskite solution to the first polymer solution is 1:(1-30).

[0046] The perovskite concentration in the perovskite solution is 0.005-4.0mmol / mL, and the perovskite is AX and PbX 2 A mixture of AX and PbX 2 The molar ratio of is 1:(0.5-2), A is a mixture of one or more of cesium, methylamine, and ethylamine, and X is a mixture of one or more of I, Cl, and Br. The solvent of the perovskite solution is a mixture of one or more of DMF, DMSO, NMP, and GBL.

[0047] The first polymer in the first polymer solution is PU, PAN or PVC, the concentration of the first polymer is 5-50wt%, and the solvent of the first polymer solution is a mixture of one or more of DMF, DMSO, NMP and GBL.

[0048] S2, dissolving the conductive material and the second polymer in a solvent to obtain a uniform composite conductive spinning solution.

[0049] In some embodiments, the conductive material is a mixture of one or more carbon-based conductive materials, organic conductive materials, and metal materials. Further, the carbon-based conductive material is a mixture of one or more of CNT, CB, graphene, and MXene. The organic conductive material is a mixture of one or more of MEH-PPV, poly (3-hexylthiophene), and polytriarylamine. The metal material is a mixture of one or more of AgNW, silver nanoparticles, and gold nanorods. The concentration of the conductive material in the composite conductive spinning solution is 0.1-20wt%.

[0050] In some embodiments, the second polymer is PAAS, PEG, PMMA or PDMS, and the concentration of the second polymer in the composite conductive spinning solution is 0.01-5 wt %. The solvent used in step S2 is water, ethanol, isopropanol, ethyl acetate, DMF, DMSO, toluene or chlorobenzene.

[0051] In some embodiments, in the composite conductive spinning solution, the hydrophilicity / hydrophobicity of the second polymer is consistent with the hydrophilicity / hydrophobicity of the conductive material and the hydrophilicity / hydrophobicity of the solvent.

[0052] S3, using a wet spinning method, extruding the perovskite polymer composite spinning solution obtained in step S1 into a coagulation bath to preliminarily solidify it into fibers to obtain a core layer, and quickly immersing the core layer in the composite conductive spinning solution obtained in step S2 before it is completely solidified and dried, so that the outside of the core layer is fully and evenly covered with the conductive layer to obtain composite fiber filaments, and then performing heat treatment to dry and solidify the composite fiber filaments and further crystallize the core layer material, and after natural cooling, a visual conductive line with a skin-core structure is obtained.

[0053] In some embodiments, the coagulation bath is water at room temperature. The heat treatment temperature of the composite fiber filaments is less than or equal to 180°C. Further, the heat treatment temperature is 50-180°C, and the heat treatment time is adjusted within the range of 10min-24h according to the heat treatment temperature. Specifically, the heat treatment time is shortened as the heat treatment temperature increases, and is prolonged as the heat treatment temperature decreases. In the actual preparation process, it is sufficient to ensure that the composite fiber filaments are completely dried and solidified during the heat treatment process.

[0054] Please refer to Figure 1 In the second aspect, the embodiment of the present application provides a visualized conductive wire, which is prepared according to the preparation method in the aforementioned scheme, and the visualized conductive wire is a skin-core structure. Among them, the core layer is a composite fluorescent elastic material, and the skin layer is a composite conductive material. The visualized conductive wire has a photoluminescent property, and the fluorescence emitted by the core layer under ultraviolet light penetrates the skin structure, making the fluorescence of the visualized conductive wire visible.

[0055] In some embodiments, the photoluminescent color of the visualized conductive line provided by the present application is regulated by changing the type and proportion of the X element contained in the core layer. Further, the photoluminescent color is regulated in the blue light color range, the green light color range, the red light color range and the yellow light color range.

[0056] In some embodiments, the visualized conductive wire is stored in air with constant temperature and humidity for 30 days, and the photoluminescence fluorescence intensity and fluorescence uniformity remain substantially unchanged, and the decrease rate of the fluorescence intensity is less than 5%.

[0057] In some embodiments, the resistance of the visualized conductive line provided by the present application is regulated within the range of 100Ω-1MΩ by changing the proportion of conductive material in the cortex.

[0058] In some embodiments, the visualized conductive wire is stored in air with constant temperature and humidity for 24 days, and the normalized resistance change rate is less than 10%; when the storage temperature is increased from 15°C to 45°C, the normalized resistance change rate of the visualized conductive wire is less than 10%.

[0059] In a third aspect, an embodiment of the present application provides an application of a visualized conductive thread, which is used in the fields of flexible pattern display, encryption and anti-counterfeiting, and visualization sensor preparation.

[0060] In some embodiments, the visualized conductive thread provided by the present application is applied to the field of flexible pattern display and encryption anti-counterfeiting. Visualized conductive threads with different fluorescent colors are combined with ordinary fibers and woven onto a flexible substrate to obtain a flexible pattern, and the flexible pattern presents different patterns under natural light and ultraviolet light. Combining a specific pattern presented under ultraviolet light with a specific arrangement and combination can obtain a specific number combination or a specific letter combination / word.

[0061] Some specific embodiments are listed below. It should be noted that the embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. If specific techniques or conditions are not specified in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. The reagents or instruments used without specifying the manufacturer are all conventional products that can be obtained commercially.

[0062] Example 1

[0063] Embodiment 1 provides a method for preparing a visualized conductive line, comprising the following steps:

[0064] S1, first, prepare the perovskite solution, the specific steps are as follows: CsBr and PbBr 2 The perovskite was mixed in a molar ratio of 1:1, and the perovskite was added to a DMF-DMSO mixed solvent (V DMF :V DMSO =9:1) to obtain a perovskite solution with a concentration of 0.04 mmol / mL. Then, a first polymer solution (PU solution) was prepared by adding PU to a DMF-DMSO mixed solvent (V DMF :V DMSO =9:1) to obtain a PU solution with a concentration of 20 wt%. Finally, the perovskite solution and the PU solution are uniformly mixed in a volume ratio of 2:5 to obtain a perovskite polymer composite spinning solution.

[0065] S2, CNT and CB are mixed at a molar ratio of 10:1 to obtain a conductive material. The conductive material and the second polymer PAAS are added to deionized water and mixed evenly to obtain a composite conductive spinning solution with a conductive material concentration of 1 wt% and a PAAS concentration of 0.75 wt%.

[0066] S3, using a wet spinning method, extruding the perovskite polymer composite spinning solution obtained in step S1 into a coagulation bath (water at room temperature) to initially solidify into fibers to obtain a core layer, and quickly immersing the core layer in the composite conductive spinning solution obtained in step S2 when the core layer is not completely solidified and dried, so that the core layer is fully and evenly coated with a conductive layer to obtain a composite fiber filament, and then heat-treating it at 60° C. for 0.5 h to dry and solidify the composite fiber filament. At the same time, the heat treatment also promotes the crystallization of the perovskite material in the light-emitting layer (core layer). After natural cooling, a visual conductive line with a skin-core structure is obtained.

[0067] The photoluminescence color of the visualized conductive wire prepared in Example 1 is green light. The performance of the visualized conductive wire prepared in Example 1 is tested as follows:

[0068] (1) The initial resistance of the visualized conductive line was tested to be 80±3 kΩ.

[0069] (2) The visualized conductive wire was placed in air at a temperature of 15°C and a relative humidity of 69% for 24 days, and the normalized resistance change of the visualized conductive wire during the storage process was tested. The test results are shown in Figure 2 As shown, it can be seen that the visualized conductive wire prepared in Example 1 has good storage stability. After being stored in the air for 24 days, the normalized resistance change rate is 4%.

[0070] (3) The visualized conductive wire is placed in air with a relative humidity of 69%, and the ambient temperature is raised from 15°C to 45°C. The normalized resistance change of the visualized conductive wire during the temperature rise process is tested. The test results are shown in Figure 3 As shown, it can be seen that the visualized conductive wire prepared in Example 1 has good temperature stability. When the temperature rises from 15° C. to 45° C., the normalized resistance change rate is 4%.

[0071] Example 2

[0072] The difference between Example 2 and Example 1 is that in step S1, the perovskite is CsPbCl 1.5 Br 1.5 The rest is basically the same as in Example 1 and will not be described again. The photoluminescent color of the visualized conductive wire prepared in Example 2 is blue light.

[0073] Example 3

[0074] The difference between Example 3 and Example 1 is that in step S1, the perovskite is MAPbI 3 (MA refers to ammonium ion), and the rest is basically the same as in Example 1, which will not be described again. The photoluminescent color of the visualized conductive line prepared in Example 1 is red light.

[0075] The visualized conductive wires prepared in Examples 1-3 were placed in air at a temperature of 15°C and a relative humidity of 69% for 30 days, and the changes in the photoluminescence properties of the visualized conductive wires after 30 days of storage were recorded using a fluorescence microscope. Figure 4 As shown, it is a fluorescence microscope image of the visualized conductive wires prepared in Examples 1-3, from left to right are Example 1 (green), Example 2 (blue), and Example 3 (red), wherein, Figure 4 (a) Figure 4 (c) Figure 4 (e) Fluorescence microscopy image of the visualized conductive wire after 0 day of storage in air;

[0076] Figure 4 (b) Figure 4 (d) Figure 4 (f) is a fluorescence microscope image of the visualized conductive wire after being stored in the air for 30 days. It can be seen that the visualized conductive wires prepared in Examples 1-3 all have good fluorescence stability. After being stored in the air for 30 days, the fluorescence intensity and fluorescence uniformity remain basically unchanged. The decrease rate of the fluorescence intensity is shown in the table below.

[0077] project Fluorescence intensity decrease rate (%) Example 1 3.0 Example 2 3.5 Example 3 4.5

[0078] Application Example 1

[0079] Application Example 1 provides an application of a visualized conductive thread in the field of flexible pattern display and anti-counterfeiting, wherein the visualized conductive thread prepared in Examples 1-3 is woven onto a flexible substrate to obtain different patterns. Under ultraviolet light, a specific number combination or word can be obtained in combination with a specific arrangement and combination.

[0080] (1) Please refer to Figure 5 In (a), (b), and (c), the visualized conductive thread prepared in Example 1 is used to weave a digital pattern 2, the visualized conductive thread prepared in Example 3 is used to weave a digital pattern 6, and the visualized conductive thread prepared in Example 2 is used to weave a digital pattern 7, and then the digital pattern 267 is supplemented with ordinary fibers to weave a digital pattern 888. With this arrangement, the number seen under natural light is 888, and the number seen under ultraviolet light is 267. After setting a specific permutation and combination, a specific digital combination can be obtained, including 267, 276, 726, 762, 627, and 672. For example, when the permutation and combination is set to red, green, and blue, the digital combination obtained is 627.

[0081] (2) Please refer to Figure 5 In (d), (e), and (f), the visualized conductive thread prepared in Example 1 is used to weave the letter pattern O, the visualized conductive thread prepared in Example 2 is used to weave the letter pattern E, and the visualized conductive thread prepared in Example 3 is used to weave the letter pattern N, and then the letter pattern OEN is supplemented with ordinary fiber to become POTENTIAL. In this way, the letter seen under natural light is POTENTIAL, and when the arrangement and combination is set to green, red, and blue, the letter seen under ultraviolet light is ONE.

[0082] Example 4

[0083] The difference between Example 4 and Example 1 is that in step S2, the conductive material is MEH-PPV and the second polymer is PDMS. Specifically, MEH-PPV and PDMS are added to toluene and mixed evenly to obtain a composite conductive spinning solution with a MEH-PPV concentration of 1wt% and a PDMS concentration of 0.1wt%. The rest is basically the same as Example 1 and will not be repeated here.

[0084] See also Figure 6 As shown, the visualized conductive thread prepared in Example 4 is orange under natural light and has a fluorescent color of yellow under ultraviolet light. The initial resistance of the visualized conductive thread was tested to be 100±5 kΩ. The visualized conductive thread was placed in air at a temperature of 15°C and a relative humidity of 69% for 24 days, and the normalized resistance change rate was 3%.

[0085] Example 5

[0086] The difference between Example 5 and Example 1 is that the second polymer used in step S2 is PEG, and the concentration of PEG in the composite conductive spinning solution is 0.5 wt %. The rest is basically the same as Example 1 and will not be described again.

[0087] The visualized conductive thread prepared in Example 5 is black under natural light and has a fluorescent color of green under ultraviolet light. The initial resistance of the visualized conductive thread is tested to be 90±5 kΩ. The visualized conductive thread is placed in air at a temperature of 15°C and a relative humidity of 69% for 24 days, and the normalized resistance change rate is 8%.

[0088] Example 6

[0089] The difference between Example 6 and Example 1 is that the conductive material used in step S2 is CNT, and the concentration of CNT in the composite conductive spinning solution is 12 wt %. The rest is basically the same as Example 1 and will not be described again.

[0090] The visualized conductive thread prepared in Example 6 is black under natural light and has a green fluorescent color under ultraviolet light. The initial resistance of the visualized conductive thread is tested to be 800±25Ω. The visualized conductive thread is placed in air at a temperature of 15°C and a relative humidity of 69% for 24 days, and the normalized resistance change rate is 7%.

[0091] Example 7

[0092] The difference between Example 7 and Example 1 is that the conductive material used in step S2 is CNT with a concentration of 0.5 wt %. The rest is basically the same as Example 1 and will not be described again.

[0093] The visualized conductive thread prepared in Example 7 is black under natural light and has a fluorescent color of green under ultraviolet light. The initial resistance of the visualized conductive thread is tested to be 500±20 kΩ. The visualized conductive thread is placed in air at a temperature of 15°C and a relative humidity of 69% for 24 days, and the normalized resistance change rate is 6%.

[0094] Example 8

[0095] The difference between Example 8 and Example 1 is that the conductive material used in step S2 is AgNW, and the concentration in the composite conductive spinning solution is 0.5wt%; the polymer is PVA, and the concentration in the composite conductive spinning solution is 0.5wt%. The rest is basically the same as Example 1 and will not be repeated here.

[0096] The visualized conductive wire prepared in Example 8 is silvery white under natural light and has a green fluorescent color under ultraviolet light. The initial resistance of the visualized conductive wire is tested to be 10±1 kΩ. The visualized conductive wire is placed in air at a temperature of 15°C and a relative humidity of 69% for 24 days, and the normalized resistance change rate is 8.2%.

[0097] The properties of the visualized conductive wires prepared in Examples 1-8 are summarized in the table below.

[0098]

[0099]

[0100] In summary, the present application provides a visual conductive wire and its preparation method and application. The prepared visual conductive wire is a skin-core structure, the core layer has photoluminescence performance, and the emitted fluorescence can pass through the skin layer, so that the visual conductive wire has a fluorescent display function. In addition, the fluorescent color and resistance of the visual conductive wire are adjustable, and the fluorescence intensity is high, uniformity and stability are good. The electronic temperature resistance and storage stability of the conductive layer (skin layer) are good, and it can be used in the fields of flexible pattern display, encryption and anti-counterfeiting, and preparation of visual sensors, and has good application prospects.

[0101] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and the embodiments having the same structure as the technical idea and exerting the same effect within the scope of the technical solution of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the main purpose of the present application, various modifications that can be thought of by those skilled in the art to the embodiments and other methods of combining some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. A method for preparing a visual conductive line, characterized in that: The steps include: S1, uniformly mixing the perovskite solution and the first polymer solution to obtain a perovskite polymer composite spinning solution; S2, dissolving the conductive material and the second polymer in a solvent to obtain a uniform composite conductive spinning solution; S3, using a wet spinning method, extruding the perovskite polymer composite spinning solution obtained in step S1 into a coagulation bath to preliminarily solidify it into fibers to obtain a core layer, and quickly immersing the core layer in the composite conductive spinning solution obtained in step S2 before it is completely solidified and dried, so that the outside of the core layer is fully and evenly covered with a conductive layer to obtain a composite fiber filament, and then performing a heat treatment to dry and solidify the composite fiber filament and further crystallize the core layer material, and after natural cooling, a visual conductive line with a skin-core structure is obtained.

2. The method for preparing a visualized conductive line according to claim 1, characterized in that: In the perovskite solution described in step S1, the concentration of perovskite is 0.005-4.0mmol / mL, and the perovskite is a mixture of AX and PbX2; wherein the molar ratio of AX to PbX2 is 1:(0.5-2), A is a mixture of one or more of cesium, methylamine, and ethylamine, and X is a mixture of one or more of I, Cl, and Br; the solvent of the perovskite solution is a mixture of one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and γ-butyrolactone.

3. The method for preparing a visualized conductive line according to claim 1, characterized in that: In the first polymer solution described in step S1, the first polymer is polyurethane, polyacrylonitrile or polyvinyl chloride, and the concentration of the first polymer is 5-50wt%; the solvent of the first polymer solution is a mixture of one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and γ-butyrolactone; in step S1, the volume ratio of the perovskite solution to the first polymer solution is 1:(1-30).

4. The method for preparing a visualized conductive line according to claim 1, characterized in that: In step S2, the conductive material is a mixture of one or more of a carbon-based conductive material, an organic conductive material, and a metal material; the second polymer is sodium polyacrylate, polyethylene glycol, polymethyl methacrylate, or polydimethylsiloxane; and the solvent is water, ethanol, isopropanol, ethyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, toluene, or chlorobenzene; wherein the concentration of the conductive material in the composite conductive spinning solution is 0.1-20wt%, and the concentration of the second polymer in the composite conductive spinning solution is 0.01-5wt%; in the composite conductive spinning solution, the hydrophilicity / hydrophobicity of the second polymer is consistent with the hydrophilicity / hydrophobicity of the conductive material and the hydrophilicity / hydrophobicity of the solvent.

5. The method for preparing a visualized conductive line according to claim 4, characterized in that: The carbon-based conductive material is a mixture of one or more of carbon nanotubes, carbon black, graphene, and MXene; the organic conductive material is a mixture of one or more of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylethynyl], poly(3-hexylthiophene), and polytriarylamine; the metal material is a mixture of one or more of silver nanowires, silver nanoparticles, and gold nanorods.

6. The method for preparing a visualized conductive line according to claim 1, characterized in that: In step S3, the coagulation bath is water at room temperature, and the temperature of the heat treatment is lower than or equal to 180°C.

7. A visual conductive line, characterized in that: The visualized conductive wire is prepared according to the preparation method described in any one of claims 1-6, and the visualized conductive wire is a skin-core structure; wherein the core layer is a composite fluorescent elastic material, and the skin layer is a composite conductive material; the visualized conductive wire has a photoluminescent property, and the fluorescence emitted by the core layer under ultraviolet light penetrates the skin structure, making the fluorescence of the visualized conductive wire visible.

8. The visualized conductive wire according to claim 7, characterized in that: The photoluminescence color of the visualized conductive thread is regulated by changing the type and proportion of the X element contained in the core layer; when the visualized conductive thread is stored in air with constant temperature and humidity for 30 days, the decrease rate of the photoluminescence fluorescence intensity is less than 5%.

9. The visualized conductive wire according to claim 8, characterized in that: The resistance of the visualized conductive wire is regulated by changing the proportion of conductive materials in the cortex, and the resistance regulation range is between 100Ω-1MΩ; the visualized conductive wire is stored in air with constant temperature and humidity for 24 days, and the normalized resistance change rate is less than 10%; when the storage temperature is increased from 15°C to 45°C, the normalized resistance change rate of the visualized conductive wire is less than 10%.

10. A use of a visualized conductive wire prepared by the preparation method according to any one of claims 1 to 6 or a visualized conductive wire according to any one of claims 7 to 9, characterized in that: The visualized conductive thread is used in the fields of flexible pattern display, encryption and anti-counterfeiting, and visualization sensor preparation.

Images