CN111564237B - Preparation method of near-infrared thermal-repair flexible conductive film - Google Patents
Preparation method of near-infrared thermal-repair flexible conductive film Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 124
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 116
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052709 silver Inorganic materials 0.000 claims abstract description 83
- 239000004332 silver Substances 0.000 claims abstract description 83
- 239000007788 liquid Substances 0.000 claims abstract description 61
- 239000002131 composite material Substances 0.000 claims abstract description 60
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 47
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 31
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 28
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 28
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 28
- 230000008439 repair process Effects 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 26
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 25
- 238000004729 solvothermal method Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000011268 mixed slurry Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 30
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- 230000009471 action Effects 0.000 abstract description 2
- -1 silver nitrate ions Chemical class 0.000 description 29
- 239000000243 solution Substances 0.000 description 27
- 239000002042 Silver nanowire Substances 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 239000013078 crystal Substances 0.000 description 22
- 239000011259 mixed solution Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- 238000005266 casting Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- LYCAIKOWRPUZTN-NMQOAUCRSA-N 1,2-dideuteriooxyethane Chemical compound [2H]OCCO[2H] LYCAIKOWRPUZTN-NMQOAUCRSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 238000010405 reoxidation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Abstract
The invention provides a near-infrared thermal-repair flexible conductive film and a preparation method thereof, belonging to the technical field of self-repair materials. The preparation method comprises the following steps: mixing graphene oxide, silver nitrate and ethylene glycol to obtain a first mixed feed liquid; mixing polyvinylpyrrolidone, ferric trichloride and ethylene glycol to obtain a second mixed feed liquid; mixing the first mixed feed liquid and the second mixed feed liquid, and carrying out solvothermal reaction on the obtained reaction feed liquid to obtain a silver nanowire-graphene composite material; and mixing the silver nanowire-graphene composite material, thermoplastic polyurethane and N, N-dimethylformamide, forming a film by using the obtained mixed slurry, and drying to obtain the near-infrared thermal repair flexible conductive film. The conductive film prepared by the invention has high electrical conductivity and thermal conductivity, has high repair efficiency under the action of near infrared light, and can realize rapid and repeated repair.
Description
Technical Field
The invention relates to the technical field of self-repairing materials, in particular to a near-infrared thermal repairing flexible conductive film and a preparation method thereof.
Background
In recent years, with the development of portable electronic devices and flexible wearable electronic devices, flexible electrodes have become a hot point of research as an important component of electronic devices. However, when the electrode is used, micro cracks or micro damages are easily generated due to repeated abrasion, bending, impact or scraping, so that the device cannot normally work, even becomes electronic waste. With the improvement of environmental awareness and the continuous deepening of sustainable development concept, the development of a flexible electrode with a self-repairing function is urgently needed, the intelligent repair of microcracks or micro-damage of materials is realized, and the basic functions of the materials are recovered, so that the reliability of a device is improved, the service life is prolonged, the reuse rate of the device is improved, and the like.
However, due to the special requirements of electronic devices on electricity, heat, force, environment and the like, only a few self-repairing material systems can be applied to the electronic field. At present, self-repairing electronic materials and application research thereof are still in the research and development stage.
Disclosure of Invention
The invention aims to provide a near-infrared thermal repair flexible conductive film and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a near-infrared thermal repair flexible conductive film, which comprises the following steps:
mixing graphene oxide, silver nitrate and ethylene glycol to obtain a first mixed feed liquid;
mixing polyvinylpyrrolidone, ferric trichloride and ethylene glycol to obtain a second mixed feed liquid;
mixing the first mixed feed liquid and the second mixed feed liquid, and carrying out solvothermal reaction on the obtained reaction feed liquid to obtain a silver nanowire-graphene composite material;
and mixing the silver nanowire-graphene composite material, thermoplastic polyurethane and N, N-dimethylformamide, forming a film by using the obtained mixed slurry, and drying to obtain the near-infrared thermal repair flexible conductive film.
Preferably, the temperature of the solvothermal reaction is 150-180 ℃ and the time is 3-5 hours.
Preferably, in the reaction liquid, the mass content of silver nitrate is 0.5-1.0%, and the mass ratio of graphene oxide to silver nitrate is (0.03-0.1): 1, the mass content of polyvinylpyrrolidone is 1.0-1.3%, and the mass content of ferric trichloride is 0.0015-0.003%.
Preferably, the mass of the silver nanowire-graphene composite material accounts for 20-40% of the total mass of the silver nanowire-graphene composite material and the thermoplastic polyurethane.
Preferably, the mass of the thermoplastic polyurethane accounts for 20-30% of the total mass of the thermoplastic polyurethane and the N, N-dimethylformamide.
Preferably, the film forming mode is casting film forming.
Preferably, the drying temperature is 60-75 ℃, and the drying time is 12-36 hours.
Preferably, the mixing of the graphene oxide, the silver nitrate and the ethylene glycol comprises: adding graphene oxide into ethylene glycol for ultrasonic treatment, then adding silver nitrate and stirring until the graphene oxide is completely dissolved.
The invention provides a near-infrared thermal repair flexible conductive film prepared by the preparation method in the scheme, which comprises a silver nanowire-graphene composite material and thermoplastic polyurethane.
Preferably, the mass content of the silver nanowire-graphene composite material is 20-40%, and the balance is thermoplastic polyurethane.
The invention provides a preparation method of a near-infrared thermal repair flexible conductive film, which comprises the following steps: mixing graphene oxide, silver nitrate and ethylene glycol to obtain a first mixed feed liquid; mixing polyvinylpyrrolidone, ferric trichloride and ethylene glycol to obtain a second mixed feed liquid; mixing the first mixed feed liquid and the second mixed feed liquid, and carrying out solvothermal reaction on the obtained reaction feed liquid to obtain a silver nanowire-graphene composite material; and mixing the silver nanowire-graphene composite material, thermoplastic polyurethane and N, N-dimethylformamide, forming a film by using the obtained mixed slurry, and drying to obtain the near-infrared thermal repair flexible conductive film.
According to the invention, graphene oxide, silver nitrate and ethylene glycol are mixed, silver nitrate ions can be adsorbed on the surface and between layers of a graphene oxide sheet to form a graphene oxide/silver ion composite system, and in the subsequent solvothermal reaction process, when silver ions in the graphene oxide/silver ion composite system are reduced to form silver nanowires, the graphene oxide is also reduced to graphene, so that the silver nanowires are favorably attached to the surface of the graphene and inserted between the layers of the graphene when being formed, and a silver nanowire-graphene hybrid structure is formed. The silver nanowire-graphene hybrid structure avoids the stacking of graphene sheet layers, improves the dispersibility, is favorable for improving the conductivity of the film, and makes up the influence of the silver nanowire on the mechanical property of the conductive film. The method comprises the steps of mixing polyvinylpyrrolidone, ferric trichloride and ethylene glycol to obtain a second mixed feed liquid, wherein the polyvinylpyrrolidone is used as a surface modifier and has the functions of controlling the growth of silver nanowires and controlling the appearance, the ethylene glycol is used as a reducing agent and a solvent, and the ferric trichloride is used as an inhibitor. Specifically, the method comprises the following steps: after the first mixed feed liquid and the second mixed feed liquid are mixed, before the solvothermal reaction, a graphene oxide/silver ion composite system in the reaction feed liquid can form a small amount of silver crystal seeds with ferric trichloride and polyvinylpyrrolidone, and then the solvothermal reaction is carried out, at the initial stage of the reaction, chloride ions in the reaction feed liquid can provide electrostatic stability for the silver crystal seeds formed firstly, and the chloride ions can be combined with the silver ions to generate AgCl colloid, so that the concentration of free silver ions in the initial solution is reduced, and the speed of reduction and growth of the silver crystal seeds of the silver ions is reduced; this slow reaction process favors the formation of thermodynamically more stable multiple twin seeds; the polyvinylpyrrolidone is preferentially adsorbed on the {100} crystal face group of the multiple twin crystal seed crystal, so that the polyvinylpyrrolidone can grow along the {111} crystal face and grow into a silver nanowire through anisotropy; with the progress of the reaction, the concentration of free silver ions in the solution is gradually reduced, and in order to keep the equilibrium concentration of the silver ions and the AgCl colloid, the silver ions are gradually released from the AgCl colloid and grow into silver nanowires; with the increase of the concentration of the silver nanowires, free silver ions in the solution are further reduced, better conditions are provided for the formation and growth of multiple twin crystal seeds, and the silver nanowires with larger diameters can be obtained. Meanwhile, the graphene oxide is reduced into graphene by ethylene glycol in the solvothermal reaction process, and the formed silver nanowires are attached to the surface of the graphene and inserted into the layers of the graphene, so that the silver nanowire-graphene composite material with the hybrid structure is obtained.
Meanwhile, due to the existence of residual oxygen in the reaction feed liquid, the reaction feed liquid can generate an etching effect on the multiple twin crystal seeds to prevent the multiple twin crystal seeds from growing into silver nanowires, Fe3+Can be reduced to Fe by ethylene glycol2+And oxygen can convert Fe2+Reoxidation to Fe3+And circulating in sequence, wherein the process can consume the residual oxygen in the reaction feed liquid and eliminate the etching effect on the silver seed crystal.
According to the invention, the thermoplastic polyurethane is used as a matrix, the silver nanowire-graphene composite material with a hybrid structure is used as a conductive filler (wherein the silver nanowire is used as a main conductive phase, and the graphene is used as an auxiliary phase), and a high-efficiency energy conversion unit and a conductive path based on the silver nanowire-graphene are constructed in a thermoplastic polyurethane system, so that the obtained flexible conductive film has high conductivity; meanwhile, by utilizing the absorption characteristics of the silver nanowires and the graphene to near infrared light, the damaged thermoplastic polyurethane material can be repaired by locally heating a micro area, the repairing efficiency of the thermoplastic polyurethane conductive film can be improved, and quick and repeated repairing can be realized. Specifically, when near-infrared light irradiates the conductive film, the silver nanowire-graphene composite material absorbs the near-infrared light to heat the thermoplastic polyurethane, meanwhile, the thermoplastic polyurethane absorbs part of heat, and the thermoplastic polyurethane and the heat absorb part of heat together to realize self-repairing of the damaged film by promoting the thermoplastic polyurethane to generate melt flow, so that the repairing efficiency is greatly improved; and the silver nanowire-graphene composite material is pulled to be recombined in the self-repairing process to form a new conductive network, so that the high conductivity is still realized after the repairing is finally realized.
In addition, the graphene is beneficial to improving the mechanical property of the thermoplastic polyurethane material, so that the repaired conductive film still has good mechanical property.
The results of the embodiment show that the near-infrared thermal repair flexible conductive film prepared by the invention has high conductivity, and when microcracks appear on the surface of the conductive film, the microcracks disappear after the conductive film is irradiated for 5-10 minutes under an infrared lamp with the wavelength of 0.76-5 mu m, so that complete repair is realized.
Detailed Description
The invention provides a preparation method of a near-infrared thermal repair flexible conductive film, which comprises the following steps:
mixing graphene oxide, silver nitrate and ethylene glycol to obtain a first mixed feed liquid;
mixing polyvinylpyrrolidone, ferric trichloride and ethylene glycol to obtain a second mixed feed liquid;
mixing the first mixed feed liquid and the second mixed feed liquid, and carrying out solvothermal reaction on the obtained reaction feed liquid to obtain a silver nanowire-graphene composite material;
and mixing the silver nanowire-graphene composite material, thermoplastic polyurethane and N, N-dimethylformamide, forming a film by using the obtained mixed slurry, and drying to obtain the near-infrared thermal repair flexible conductive film.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
According to the invention, graphene oxide, silver nitrate and ethylene glycol are mixed to obtain a first mixed feed liquid.
In the present invention, the mixing process is preferably: adding graphene oxide into ethylene glycol for ultrasonic treatment, then adding silver nitrate and stirring until the graphene oxide is completely dissolved. In the present invention, the power of the ultrasound is preferably 300W, and the time of the ultrasound is preferably 1 hour. The graphene oxide is uniformly dispersed into the ethylene glycol through ultrasound. The invention has no special requirement on the stirring condition, and can ensure that the silver nitrate is completely dissolved. The present invention will be described later with respect to the amounts of the respective raw materials.
In the mixing process, silver nitrate ions can be adsorbed on the surface and the layers of the graphene oxide sheet layer to form a graphene oxide/silver ion composite system, and in the subsequent solvothermal reaction process, when silver ions in the graphene oxide/silver ion composite system are reduced to form silver nanowires, the graphene oxide is also reduced to graphene, so that the silver nanowires are favorably attached to the surface of the graphene and inserted into the layers of the graphene during formation, and a silver nanowire-graphene hybrid structure is formed.
The invention mixes polyvinylpyrrolidone, ferric trichloride and glycol to obtain a second mixed feed liquid. According to the invention, preferably, the polyvinylpyrrolidone is added into the ethylene glycol and stirred until the polyvinylpyrrolidone is completely dissolved, and then the ferric chloride is added and stirred until the polyvinylpyrrolidone is completely dissolved, so that a second mixed feed liquid is obtained. The invention has no special requirements on each stirring condition, and can ensure that each substance is completely dissolved. In the present invention, polyvinylpyrrolidone as a surface modifier has the function of controlling the growth and morphology of silver nanowires, ethylene glycol as a reducing agent and a solvent, ferric chloride as an inhibitor, and the specific functions and the amounts of the substances will be discussed in detail later.
After the first mixed feed liquid and the second mixed feed liquid are obtained, the first mixed feed liquid and the second mixed feed liquid are mixed to obtain the reaction feed liquid.
In the reaction liquid, the mass content of silver nitrate is preferably 0.5-1.0%, and more preferably 0.6-0.9%; the mass ratio of the graphene oxide to the silver nitrate is preferably (0.03-0.1): 1, more preferably (0.05 to 0.1): 1; the mass content of the polyvinylpyrrolidone is preferably 1.0-1.3%, more preferably 1.1-1.2%; the mass content of the ferric trichloride is preferably 0.0015-0.003%, and more preferably 0.002-0.0025%. The mass of the ethylene glycol in the first mixed feed liquid and the second mixed feed liquid is preferably equal. The graphene oxide has no special requirement, and the graphene oxide which is industrially universal can be adopted (is multilayer graphene oxide).
The invention controls the content of polyvinylpyrrolidone in the reaction liquid in the above range, which is beneficial to better controlling the growth of silver nanowires, and when the content of polyvinylpyrrolidone is too high or too low, nano silver particles or a mixture of particles, wires and rods is easily formed.
According to the invention, after the first mixed feed liquid and the second mixed feed liquid are mixed, the graphene oxide/silver ion composite system can form a small amount of silver seed crystals with ferric trichloride and polyvinylpyrrolidone.
After reaction liquid is obtained, the reaction liquid is subjected to solvothermal reaction to obtain the silver nanowire-graphene composite material.
In the invention, the reaction liquid is preferably placed in a reaction kettle, and then the reaction kettle is placed in a vacuum drying oven for solvothermal reaction.
In the invention, the temperature of the solvothermal reaction is preferably 150-180 ℃, and more preferably 160-170 ℃; the solvothermal reaction time is preferably 3 to 5 hours, and more preferably 3.5 to 4.5 hours.
In the initial stage of the reaction, chloride ions in the reaction liquid can provide electrostatic stability for the silver seed crystal formed firstly, and the chloride ions can be combined with the silver ions to generate AgCl colloid, so that the concentration of free silver ions in the initial solution is reduced, and the speed of reduction of the silver ions and growth of the silver seed crystal is reduced; this slow reaction process favors the formation of thermodynamically more stable multiple twin seeds; the polyvinylpyrrolidone is preferentially adsorbed on the {100} crystal face group of the multiple twin crystal seed crystal, so that the polyvinylpyrrolidone can grow along the {111} crystal face and grow into a silver nanowire through anisotropy; with the progress of the reaction, the concentration of free silver ions in the solution is gradually reduced, and in order to keep the equilibrium concentration of the silver ions and the AgCl colloid, the silver ions are gradually released from the AgCl colloid and grow into silver nanowires; with the increase of the concentration of the silver nanowires, free silver ions in the solution are further reduced, better conditions are provided for the formation and growth of multiple twin crystal seeds, and the silver nanowires with larger diameters can be obtained. Meanwhile, the graphene oxide is reduced into graphene by ethylene glycol in the solvothermal reaction process, and the formed silver nanowires are attached to the surface of the graphene and inserted into the layers of the graphene, so that the silver nanowire-graphene composite material with the hybrid structure is obtained. Meanwhile, due to the existence of residual oxygen in the reaction liquid, the etching effect is generated on the multiple twin crystal seeds to prevent the growth of the multiple twin crystal seeds into silver nanowires and Fe3+Can be reduced to Fe by ethylene glycol2+And oxygen can convert Fe2+Reoxidation to Fe3+And circulating in sequence, wherein the process can consume the residual oxygen in the reaction feed liquid and eliminate the etching effect on the silver seed crystal.
After the solvothermal reaction is completed, the method preferably further comprises naturally cooling and washing the system after the reaction. In the invention, the washing process is preferably to add acetone into a product system after natural cooling for centrifugal washing twice, and then adopt ethanol for centrifugal washing twice to obtain slurry. The invention utilizes acetone to wash out glycol in the product system. The silver nanowire-graphene composite material exists in the slurry, preferably, drying is not carried out, and the subsequent steps are directly carried out on the slurry obtained by centrifuging ethanol, so that the silver nanowire-graphene composite material is prevented from being agglomerated after being dried. The invention has no special requirement on the solid content of the slurry, and the ethanol in the slurry can volatilize after the film is formed.
After the silver nanowire-graphene composite material is obtained, the silver nanowire-graphene composite material, thermoplastic polyurethane and N, N-dimethylformamide are mixed to obtain mixed slurry.
In the invention, the mass of the thermoplastic polyurethane is preferably 20-30% of the total mass of the thermoplastic polyurethane and the N, N-dimethylformamide; the mass of the silver nanowire-graphene composite material is preferably 20-40% of the total mass of the silver nanowire-graphene composite material and the thermoplastic polyurethane.
According to the invention, preferably, the thermoplastic polyurethane is added into N, N-dimethylformamide, then the silver nanowire-graphene composite material is added, and the mixture is stirred by a nano-dispersion machine to obtain the mixed slurry. In the invention, the rotation speed of the nano-dispersion machine is preferably 2000-4000 rpm, and more preferably 3000 rpm; the stirring treatment time is preferably 0.5 to 2 hours, and more preferably 1 hour. In the present invention, the temperature of the stirring treatment is preferably not more than 30 ℃. Compared with mixed slurry obtained by other mixing methods, the mixed slurry obtained by adopting the nano dispersion machine is more uniform and has better film forming state.
After the mixed slurry is obtained, the mixed slurry is subjected to film forming and drying to obtain the near-infrared thermal repair flexible conductive film.
In the present invention, the film formation is preferably performed by casting film formation. The invention preferably performs casting film formation on a polytetrafluoroethylene plate. The invention has no special requirement on the thickness of the casting film and can control the thickness according to the actual requirement. In the invention, the drying temperature is preferably 60-75 ℃, and the drying time is preferably 12-36 hours. In the drying process, the N, N-dimethylformamide is evaporated, and the near-infrared thermal repairing flexible conductive film is obtained.
The invention provides a near-infrared thermal repair flexible conductive film prepared by the preparation method in the scheme, which comprises a silver nanowire-graphene composite material and thermoplastic polyurethane. In the invention, the mass content of the silver nanowire-graphene composite material in the near-infrared thermal repair flexible conductive film is preferably 20-40%, and the balance is thermoplastic polyurethane. In the invention, the thickness of the near-infrared thermal repair flexible conductive film is preferably 30-800 μm. According to the invention, the thermoplastic polyurethane is used as a matrix, the silver nanowire-graphene composite material with a hybrid structure is used as a conductive filler (wherein the silver nanowire is used as a main conductive phase, and the graphene is used as an auxiliary phase), and a high-efficiency energy conversion unit and a conductive path based on the silver nanowire-graphene are constructed in a thermoplastic polyurethane system, so that the obtained flexible conductive film has high conductivity; meanwhile, by utilizing the absorption characteristics of the silver nanowires and the graphene to near infrared light, the damaged thermoplastic polyurethane material can be repaired by locally heating a micro area, the repairing efficiency of the thermoplastic polyurethane conductive film can be improved, and quick and repeated repairing can be realized. Specifically, when near-infrared light irradiates the conductive film, the silver nanowire-graphene composite material absorbs the near-infrared light to heat the thermoplastic polyurethane, meanwhile, the thermoplastic polyurethane absorbs part of heat, and the thermoplastic polyurethane and the heat absorb part of heat together to realize self-repairing of the damaged film by promoting the thermoplastic polyurethane to generate melt flow, so that the repairing efficiency is greatly improved; and the silver nanowire-graphene composite material is pulled to be recombined in the self-repairing process to form a new conductive network, so that the high conductivity is still realized after the repairing is finally realized.
The present invention provides a near infrared thermal repair flexible conductive film and a method for manufacturing the same, which are described in detail below with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding 0.068 g of graphene oxide into 40 ml of ethylene glycol solution, performing ultrasonic treatment at 300W for 1 hour, adding 0.68 g of silver nitrate into the solution, and stirring until the silver nitrate is completely dissolved to obtain a first mixed solution; adding 1.019 g of polyvinylpyrrolidone (K30) into 40 ml of ethylene glycol, stirring until the polyvinylpyrrolidone is completely dissolved, then adding 0.0016 g of ferric trichloride into the ethylene glycol, and stirring until the ferric trichloride is completely dissolved to obtain a second mixed feed liquid; pouring the first mixed material liquid into the second mixed material liquid, quickly stirring for 30 seconds, and pouring the mixed solution into a reaction kettle; and (3) putting the reaction kettle into a vacuum drying oven for reaction at 160 ℃ for 3 hours, naturally cooling, and respectively centrifugally washing twice with acetone and ethanol in sequence to obtain the silver-containing nanowire-graphene composite material slurry (the solvent is ethanol).
500 ml of N, N-dimethylformamide solution of thermoplastic polyurethane with the mass concentration of 30% is prepared, and then the slurry containing the silver nanowire-graphene composite material (containing 45 g of the silver nanowire-graphene composite material, wherein the mass percentage content of the silver nanowire-graphene composite material in the conductive film is 30%) is added into the thermoplastic polyurethane solution; stirring the mixed solution by using a nano dispersion machine for 1 hour at the rotating speed of 3000rpm, and controlling the temperature not to exceed 30 ℃; and then casting the mixed solution on a polytetrafluoroethylene plate to form a film, and then carrying out heat treatment on the polytetrafluoroethylene plate at the temperature of 70 ℃ for 12 hours on a heating plate until the quality is unchanged, thereby obtaining the conductive film. The conductive film had a thickness of about 200 μm and a resistivity of 1.2. omega. mm.
Scratching a flaw with the length of 3 cm and the depth of 5 mm on the surface of the conductive film by using an art designer, then putting the conductive film under an infrared lamp (a Philips infrared lamp bulb with the power of 250W, the wavelength of 0.76-5 mu m and the peak wavelength of 4 mu m) for heat treatment for 5 minutes, wherein the flaw disappears, self-repairing is realized, and the resistivity of the conductive film after the repairing is measured to be 1.31 omega mm, which shows that the conductive film prepared by the method can realize quick repairing; the above process was repeated 5 more times at the repaired flaw, and the resistivity of the conductive film after repair was 1.28 Ω · mm, 1.32 Ω · mm, 1.39 Ω · mm, 1.43 Ω · mm, and 1.49 Ω · mm, respectively. The conductive film prepared by the method still has good conductivity after being repaired for many times.
Example 2
Adding 0.034 g of graphene oxide into 40 ml of ethylene glycol solution, performing ultrasonic treatment at 300W for 1 hour, adding 0.68 g of silver nitrate into the solution, and stirring until the silver nitrate is completely dissolved to obtain a first mixed solution; adding 1.019 g of polyvinylpyrrolidone (K30) into 40 ml of ethylene glycol, stirring until the polyvinylpyrrolidone is completely dissolved, then adding 0.0016 g of ferric trichloride into the ethylene glycol, and stirring until the ferric trichloride is completely dissolved to obtain a second mixed feed liquid; pouring the first mixed material liquid into the second mixed material liquid, quickly stirring for 30 seconds, and pouring the mixed solution into a reaction kettle; and (3) putting the reaction kettle into a vacuum drying oven for reaction at 160 ℃ for 3 hours, naturally cooling, and respectively centrifugally washing twice with acetone and ethanol in sequence to obtain the silver-containing nanowire-graphene composite material slurry (the solvent is ethanol).
500 ml of N, N-dimethylformamide solution of thermoplastic polyurethane with the mass concentration of 30% is prepared, and then the slurry containing the silver nanowire-graphene composite material (containing 30 g of the silver nanowire-graphene composite material, wherein the mass percentage content of the silver nanowire-graphene composite material in the conductive film is 20%) is added into the thermoplastic polyurethane solution; stirring the mixed solution by using a nano dispersion machine for 1 hour at the rotating speed of 3000rpm, and controlling the temperature not to exceed 30 ℃; and then casting the mixed solution on a polytetrafluoroethylene plate to form a film, and then carrying out heat treatment on the polytetrafluoroethylene plate at the temperature of 70 ℃ for 12 hours on a heating plate until the quality is unchanged, thereby obtaining the conductive film. The thickness of the conductive film was about 200 μm, and the resistivity of the conductive film was 312.7. omega. mm.
And (3) scribing cracks with a length of 3 cm and a depth of 5 mm on the surface of the conductive film by using an art designer knife, then placing the conductive film under an infrared lamp (a Philips infrared lamp bulb with the power of 250W, the wavelength of 0.76-5 mu m and the peak wavelength of 4 mu m) for heat treatment for 5 minutes, wherein the cracks disappear, self-repairing is realized, and the resistivity of the conductive film after repairing is measured to be 315.1 omega mm. The above process was repeated 5 more times on the repaired scar, and the resistivity of the conductive film after repair was 317.9 Ω · mm, 313.6 Ω · mm, 318.1 Ω · mm, 316.8 Ω · mm, and 313.8 Ω · mm, respectively. The conductive film prepared by the method still has good conductivity after being repaired for many times.
Example 3
Adding 0.034 g of graphene oxide into 40 ml of ethylene glycol solution, performing ultrasonic treatment at 300W for 1 hour, adding 0.68 g of silver nitrate into the solution, and stirring until the silver nitrate is completely dissolved to obtain a first mixed solution; adding 1.019 g of polyvinylpyrrolidone (K30) into 40 ml of ethylene glycol, stirring until the polyvinylpyrrolidone is completely dissolved, then adding 0.0016 g of ferric trichloride into the ethylene glycol, and stirring until the ferric trichloride is completely dissolved to obtain a second mixed feed liquid; pouring the first mixed material liquid into the second mixed material liquid, quickly stirring for 30 seconds, and pouring the mixed solution into a reaction kettle; and (3) putting the reaction kettle into a vacuum drying oven for reaction at 160 ℃ for 3 hours, naturally cooling, and respectively centrifugally washing twice with acetone and ethanol in sequence to obtain the silver-containing nanowire-graphene composite material slurry (the solvent is ethanol).
500 ml of N, N-dimethylformamide solution of thermoplastic polyurethane with the mass concentration of 30% is prepared. Then adding the slurry containing the silver nanowire-graphene composite material (containing 60 g of the silver nanowire-graphene composite material, wherein the mass percentage of the silver nanowire-graphene composite material in the conductive film is 40%) into a thermoplastic polyurethane solution; stirring the mixed solution by using a nano dispersion machine for 1 hour at the rotating speed of 3000rpm, and controlling the temperature not to exceed 30 ℃; and then casting the mixed solution on a polytetrafluoroethylene plate to form a film, and then carrying out heat treatment on the polytetrafluoroethylene plate at the temperature of 70 ℃ for 12 hours on a heating plate until the quality is unchanged, thereby obtaining the conductive film. The thickness of the conductive film was about 200 μm, and the resistivity of the conductive film was 0.07. omega. mm.
And (3) scribing cracks with a length of 3 cm and a depth of 5 mm on the surface of the conductive film by using an art designer knife, then placing the conductive film under an infrared lamp (a Philips infrared lamp bulb with the power of 250W, the wavelength of 0.76-5 mu m and the peak wavelength of 4 mu m) for heat treatment for 5 minutes, wherein the cracks disappear, self-repairing is realized, and the resistivity of the conductive film after repairing is measured to be 0.11 omega mm. The above process was repeated 5 more times at the repaired flaw, and the resistivity of the conductive film after repair was 0.18 Ω · mm, 0.09 Ω · mm, 0.14 Ω · mm, 0.12 Ω · mm, and 0.11 Ω · mm, respectively. The conductive film prepared by the method still has good conductivity after being repaired for many times.
Example 4
Adding 0.02 g of graphene oxide into 40 ml of ethylene glycol solution, performing ultrasonic treatment for 1 hour at 300W, adding 0.68 g of silver nitrate into the solution, and stirring until the silver nitrate is completely dissolved to obtain a first mixed solution; adding 1.019 g of polyvinylpyrrolidone (K30) into 40 ml of ethylene glycol, stirring until the polyvinylpyrrolidone is completely dissolved, then adding 0.0016 g of ferric trichloride into the ethylene glycol, and stirring until the ferric trichloride is completely dissolved to obtain a second mixed feed liquid; pouring the first mixed material liquid into the second mixed material liquid, quickly stirring for 30 seconds, and pouring the mixed solution into a reaction kettle; and (3) putting the reaction kettle into a vacuum drying oven for reaction for 3 hours at 160 ℃, naturally cooling, and respectively centrifugally washing twice with acetone and ethanol in sequence to obtain the silver nanowire-graphene composite material-containing slurry.
500 ml of N, N-dimethylformamide solution of thermoplastic polyurethane with the mass concentration of 30% is prepared, and then the slurry containing the silver nanowire-graphene composite material (containing 60 g of the silver nanowire-graphene composite material, wherein the mass percentage content of the silver nanowire-graphene composite material in the conductive film is 40%) is added into the thermoplastic polyurethane solution; stirring the mixed solution by using a nano dispersion machine for 1 hour at the rotating speed of 3000rpm, and controlling the temperature not to exceed 30 ℃; and then casting the mixed solution on a polytetrafluoroethylene plate to form a film, and then carrying out heat treatment on the polytetrafluoroethylene plate at the temperature of 70 ℃ for 12 hours on a heating plate until the quality is unchanged, thereby obtaining the conductive film. The thickness of the conductive film was about 200 μm, and the resistivity of the conductive film was 0.15. omega. mm.
And (3) scribing cracks with a length of 3 cm and a depth of 5 mm on the surface of the conductive film by using an art designer knife, then placing the conductive film under an infrared lamp (a Philips infrared lamp bulb with the power of 250W, the wavelength of 0.76-5 mu m and the peak wavelength of 4 mu m) for heat treatment for 5 minutes, wherein the cracks disappear, self-repairing is realized, and the resistivity of the conductive film after repairing is measured to be 0.19 omega mm. The above process was repeated 5 more times at the repaired flaw, and the resistivity of the conductive film after repair was 0.18 Ω · mm, 0.16 Ω · mm, 0.19 Ω · mm, 0.21 Ω · mm, and 0.20 Ω · mm, respectively. The conductive film prepared by the method still has good conductivity after being repaired for many times.
Example 5
Adding 0.068 g of graphene oxide into 40 ml of ethylene glycol solution, performing ultrasonic treatment at 300W for 1 hour, adding 0.68 g of silver nitrate into the solution, and stirring until the silver nitrate is completely dissolved to obtain a first mixed solution; adding 1.019 g of polyvinylpyrrolidone (K30) into 40 ml of ethylene glycol, stirring until the polyvinylpyrrolidone is completely dissolved, then adding 0.0016 g of ferric trichloride into the ethylene glycol, and stirring until the ferric trichloride is completely dissolved to obtain a second mixed feed liquid; pouring the first mixed material liquid into the second mixed material liquid, quickly stirring for 30 seconds, and pouring the mixed solution into a reaction kettle; and (3) putting the reaction kettle into a vacuum drying oven for reaction for 3 hours at 160 ℃, naturally cooling, and respectively centrifugally washing twice with acetone and ethanol in sequence to obtain the silver nanowire-graphene composite material-containing slurry.
500 ml of N, N-dimethylformamide solution of thermoplastic polyurethane with the mass concentration of 30% is prepared, and then the slurry containing the silver nanowire-graphene composite material (containing 45 g of the silver nanowire-graphene composite material, wherein the mass percentage content of the silver nanowire-graphene composite material in the conductive film is 30%) is added into the thermoplastic polyurethane solution; stirring the mixed solution by using a nano dispersion machine for 1 hour at the rotating speed of 3000rpm, and controlling the temperature not to exceed 30 ℃; and then casting the mixed solution on a polytetrafluoroethylene plate to form a film, and then carrying out heat treatment on the polytetrafluoroethylene plate at the temperature of 70 ℃ for 12 hours on a heating plate until the quality is unchanged, thereby obtaining the conductive film. The thickness of the conductive film was about 200 μm, and the resistivity of the conductive film was 11.8. omega. mm.
And (3) scribing cracks with a length of 3 cm and a depth of 5 mm on the surface of the conductive film by using an art designer knife, then placing the conductive film under an infrared lamp (a Philips infrared lamp bulb with the power of 250W, the wavelength of 0.76-5 mu m and the peak wavelength of 4 mu m) for heat treatment for 5 minutes, wherein the cracks disappear, self-repairing is realized, and the resistivity of the conductive film after repairing is measured to be 12.2 omega mm. The above process was repeated 5 more times at the repaired flaw, and the resistivity of the conductive film after repair was 12.8 Ω · mm, 12.9 Ω · mm, 12.1 Ω · mm, 12.9 Ω · mm, and 13.1 Ω · mm, respectively. The conductive film prepared by the method still has good conductivity after being repaired for many times.
The embodiments can show that the conductive film prepared by the invention has high electrical conductivity and thermal conductivity, has high repair efficiency under the action of near infrared light, and can realize rapid multiple repair.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of a near-infrared thermal-repair flexible conductive film is characterized by comprising the following steps:
mixing graphene oxide, silver nitrate and ethylene glycol to obtain a first mixed feed liquid;
mixing polyvinylpyrrolidone, ferric trichloride and ethylene glycol to obtain a second mixed feed liquid;
mixing the first mixed feed liquid and the second mixed feed liquid, and carrying out solvothermal reaction on the obtained reaction feed liquid to obtain a silver nanowire-graphene composite material;
and mixing the silver nanowire-graphene composite material, thermoplastic polyurethane and N, N-dimethylformamide, forming a film by using the obtained mixed slurry, and drying to obtain the near-infrared thermal repair flexible conductive film.
2. The method according to claim 1, wherein the temperature of the solvothermal reaction is 150 to 180 ℃ for 3 to 5 hours.
3. The preparation method according to claim 1, wherein the mass content of silver nitrate in the reaction liquid is 0.5-1.0%, and the mass ratio of graphene oxide to silver nitrate is (0.03-0.1): 1, the mass content of polyvinylpyrrolidone is 1.0-1.3%, and the mass content of ferric trichloride is 0.0015-0.003%.
4. The preparation method according to claim 1, wherein the mass of the silver nanowire-graphene composite material accounts for 20-40% of the total mass of the silver nanowire-graphene composite material and the thermoplastic polyurethane.
5. The method according to claim 1 or 4, wherein the mass of the thermoplastic polyurethane is 20 to 30% of the total mass of the thermoplastic polyurethane and the N, N-dimethylformamide.
6. A production method according to claim 1, wherein the film formation is cast film formation.
7. The method according to claim 1, wherein the drying is carried out at a temperature of 60 to 75 ℃ for 12 to 36 hours.
8. The method of claim 1, wherein the mixing of the graphene oxide, the silver nitrate and the ethylene glycol comprises: adding graphene oxide into ethylene glycol for ultrasonic treatment, then adding silver nitrate and stirring until the graphene oxide is completely dissolved.
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