CN114822920A - Composite material and preparation method and application thereof - Google Patents
Composite material and preparation method and application thereof Download PDFInfo
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- CN114822920A CN114822920A CN202210396826.9A CN202210396826A CN114822920A CN 114822920 A CN114822920 A CN 114822920A CN 202210396826 A CN202210396826 A CN 202210396826A CN 114822920 A CN114822920 A CN 114822920A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 36
- 238000005886 esterification reaction Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 26
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- 238000010438 heat treatment Methods 0.000 claims abstract description 21
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000002042 Silver nanowire Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000010335 hydrothermal treatment Methods 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
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- 238000003828 vacuum filtration Methods 0.000 claims description 7
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- 239000012024 dehydrating agents Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
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- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 3
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- 230000008569 process Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 3
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- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000032050 esterification Effects 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 27
- 239000010408 film Substances 0.000 description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
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- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
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- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
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- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 238000005580 one pot reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- 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
- H01B5/02—Single bars, rods, wires, or strips
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- 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
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- 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
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- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
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Abstract
The application relates to the technical field of nano materials, in particular to a composite material and a preparation method and application thereof. The preparation method of the composite material comprises the following steps: providing a nano silver wire; carrying out alkali heating treatment on the nano silver wire to obtain a hydroxylated nano silver wire; carrying out esterification reaction on the hydroxylated nano silver wire and cellulose containing carboxyl in an alcohol solvent to obtain an esterification reaction product solution; and sequentially filtering and drying the esterification reaction product solution to obtain the composite material. According to the preparation method, the hydroxyl on the surface of the nano silver wire and the carboxyl on the surface of the cellulose are subjected to esterification condensation, so that the nano silver wire and the cellulose are fixedly connected through a chemical bond, the combination stability of the nano silver wire and the cellulose is remarkably superior to that of conventional physical adsorption, the prepared composite material has better stability, and meanwhile, the hydrogen bond on the surface of the cellulose is not influenced in the esterification reaction process, so that the self-repairing function is still maintained.
Description
Technical Field
The application belongs to the technical field of nano materials, and particularly relates to a composite material and a preparation method and application thereof.
Background
In recent years, with the development of intellectualization and the rapid progress of electronic technology, flexible electronic materials gradually enter the visual field of people, are materials capable of being extruded and deformed, and have wide application prospects.
The current conductive thin film materials are limited in their own conductivity and difficult to repair properties, which makes their applications have various limitations. On one hand, the conductive film material is difficult to satisfy conductivity, stability and repeated use convenience at the same time, so that the self-repairing capability of the film material is also an important consideration factor when preparing the film material with excellent conductivity and stability. On the other hand, the crease generated when part of the paper-based conductive material is bent is difficult to eliminate, so that part of the performance of the paper-based conductive material is changed, the uniformity of the material is reduced when the material is repeatedly used, and the reusability of the material is finally reduced.
Therefore, it is difficult to obtain a conductive material having good conductivity, stability and self-repairing ability.
Disclosure of Invention
The application aims to provide a composite material, a preparation method and application thereof, and aims to solve the problem of improving the composite stability of nano silver wires and cellulose.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a composite material, comprising the steps of:
providing a nano silver wire;
carrying out alkali heating treatment on the nano silver wire to obtain a hydroxylated nano silver wire;
carrying out esterification reaction on the hydroxylated nano silver wire and cellulose containing carboxyl in an alcohol solvent to obtain an esterification reaction product solution;
and sequentially filtering and drying the esterification reaction product solution to obtain the composite material.
In one embodiment, the step of subjecting the silver nanowires to an alkali heat treatment comprises: and (3) placing the nano silver wire in an alkali solution, and then stirring and heating at the temperature of 50-60 ℃.
In one embodiment, the alkali solution is selected from at least one of a sodium hydroxide solution and a potassium hydroxide solution; and/or the presence of a gas in the gas,
the heating and stirring time is 10-13 h.
In one embodiment, the step of subjecting the hydroxylated silver nanowires to an esterification reaction with a cellulose containing carboxyl groups in an alcohol solvent comprises:
dispersing the hydroxylated nano silver wire in a first alcohol solvent to obtain a nano silver wire dispersion liquid;
dispersing the cellulose containing carboxyl in a second alcohol solvent to obtain a cellulose dispersion liquid;
and mixing the nano silver wire dispersion liquid and the cellulose dispersion liquid to obtain a mixed liquid, and then carrying out hydrothermal treatment on the mixed liquid.
In one embodiment, the temperature of the hydrothermal treatment is 130-150 ℃ and the time is 25-35 min; and/or the presence of a gas in the gas,
the step of subjecting the mixed solution to hydrothermal treatment comprises: and a dehydrating agent is added into the mixed solution.
In one embodiment, the mass concentration of the nano silver wire dispersion liquid is 4-6 mg/ml, and the mass concentration of the cellulose dispersion liquid is 0.1-0.3 mg/ml; and/or the presence of a gas in the gas,
in the mixed solution, the mass ratio of the nano silver wires to the cellulose is 1: 1.5 to 2.5.
In one embodiment, the filtration treatment is vacuum filtration membrane preparation; and/or the presence of a gas in the gas,
the drying treatment step comprises vacuum drying at 30-36 ℃.
In one embodiment, the method for preparing the silver nanowire comprises the following steps:
preparing a mixed solution containing silver salt and polyvinylpyrrolidone;
and dropwise adding the mixed solution into a bottom solution containing copper chloride at 140-160 ℃, and preserving heat for 30-120 min.
In a second aspect, the present application provides a composite material prepared by the preparation method described herein.
In a third aspect, the present application provides a use of the above composite material in a flexible electronic device.
According to the preparation method of the composite material provided by the first aspect of the application, the hydroxylated nano silver wire and the cellulose containing carboxyl are subjected to esterification reaction in an alcohol solvent, and the product solution is sequentially subjected to filtration treatment and drying treatment, so that the composite material compounded by the nano silver wire and the cellulose can be obtained; in the esterification reaction step of the preparation method, hydroxyl on the surface of the nano silver wire and carboxyl on the surface of cellulose are subjected to esterification reaction condensation, so that the nano silver wire and the cellulose are fixedly connected through a chemical bond, the combination stability of the nano silver wire and the cellulose is obviously superior to that of conventional physical adsorption, the prepared composite material has better stability, and meanwhile, the hydrogen bond on the surface of the cellulose is not influenced in the esterification reaction process, so that the self-repairing function is still kept; in addition, the preparation method has simple conditions and quick reaction, and is beneficial to industrial manufacture and batch production, thereby having good application prospect.
The composite material provided by the second aspect of the application is prepared by the specific preparation method of the application, so that the composite material has excellent conductive stability and self-repairing capability, and has a good application prospect.
The third aspect of the application is based on the characteristics of the composite material obtained by the preparation method, and the composite material can be used as a conductive film to be well applied to flexible electronic devices.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic flow diagram of a method of making a composite material provided in an embodiment of the present application;
FIG. 2 is a schematic diagram illustrating a method for preparing a composite material according to an embodiment of the present disclosure;
fig. 3 is a schematic diagram of a product obtained by a method for preparing a composite material provided in an example of the present application.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "plural" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
In a first aspect, embodiments of the present application provide a method for preparing a composite material, as shown in fig. 1, the method includes the following steps:
s01: providing a nano silver wire;
s02: carrying out alkali heating treatment on the nano silver wire to obtain a hydroxylated nano silver wire;
s03: carrying out esterification reaction on the hydroxylated nano silver wire and cellulose containing carboxyl in an alcohol solvent to obtain an esterification reaction product solution;
s04: and sequentially filtering and drying the esterification reaction product solution to obtain the composite material.
The preparation method of the composite material comprises the steps of carrying out esterification reaction on the hydroxylated nano silver wire and cellulose containing carboxyl in an alcohol solvent, and sequentially filtering and drying the product solution to obtain the composite material compounded by the nano silver wire and the cellulose; in the esterification reaction step of the preparation method, hydroxyl on the surface of the nano silver wire and carboxyl on the surface of cellulose are subjected to esterification reaction condensation, so that the nano silver wire and the cellulose are fixedly connected through a chemical bond, the combination stability of the nano silver wire and the cellulose is obviously superior to that of conventional physical adsorption, the prepared composite material has better stability, and meanwhile, the hydrogen bond on the surface of the cellulose is not influenced in the esterification reaction process, so that the self-repairing function is still kept; in addition, the preparation method has simple conditions and quick reaction, and is beneficial to industrial manufacture and batch production.
According to the preparation method, the nano silver wire and the cellulose are fixed through chemical bonds (the covalent bond energy is far greater than that of a hydrogen bond) based on the esterification reaction, so that the obtained composite material has better stability, the resistance change of the composite material after repeated bending for many times is very small, the composite material can still keep good conductivity after long-term use, and the conductive stability is remarkably superior to the physical adsorption (hydrogen bond) between the conventional nano silver wire and the cellulose. The cellulose has self-repairing performance, the state before the damage can be recovered by dripping a small amount of water after the damage, and the self-repairing function is still remained because the hydrogen bond on the surface of the cellulose is not influenced in the esterification reaction process, so that the composite material still has repairability by the preparation method. Therefore, the composite material obtained by the preparation method provided by the embodiment of the application has both conductive stability and self-repairing capability, and has a good application prospect.
In one embodiment, the silver nanowires provided above can be prepared by a polyol reduction method. Specifically, the preparation method of the nano silver wire comprises the following steps: preparing a polyalcohol solution containing silver salt and polyvinylpyrrolidone; dripping the polyhydric alcohol solution into 140-160 deg.C polyhydric alcohol base solution containing copper chloride, and keeping the temperature for 30-120 min, such as 140 deg.C, 142 deg.C, 146 deg.C, 150 deg.C, 155 deg.C, 160 deg.C, etc., for 30min, 40min, 50min, 80min, 100min, 120min, etc. The preparation method of the nano silver wire is simple to operate, low in cost and high in repeatability, and the nano silver wire with uniform size can be obtained, for example, the nano silver wire with the size of about 30 micrometers is obtained.
Further, the above-mentioned silver nanowire is prepared by using a polyol solvent selected from at least one of ethylene glycol, propylene glycol, butylene glycol and glycerol. Taking ethylene glycol as an example, silver nitrate and polyvinylpyrrolidone are dissolved in ethylene glycol to obtain an ethylene glycol solution containing silver nitrate and polyvinylpyrrolidone. In addition, a small amount of copper chloride is added into ethylene glycol to obtain a polyol base solution containing copper chloride. Heating a polyol base solution to 140-160 ℃, then dropwise adding an ethylene glycol solution containing silver nitrate and polyvinylpyrrolidone, keeping the temperature at 140-160 ℃, stirring and reacting to obtain a nano silver wire, and finally performing centrifugal separation and drying to obtain a nano silver wire solid.
In one embodiment, the step of subjecting the silver nanowires to an alkali heating treatment comprises: the nano silver wire prepared in the above way is placed in an alkali solution, and then heated and stirred at the temperature of 50-60 ℃, for example, 50 ℃, 52 ℃, 55 ℃, 60 ℃ and the like. The nano silver wire is hydroxylated through alkali heating treatment, hydroxyl is formed on the surface of the nano silver wire, and the nano silver wire can be subsequently reacted with carboxyl on the surface of cellulose, so that the nano silver wire is stably compounded on the cellulose through chemical bonds, and the composite material with better stability is obtained.
Further, the alkali solution is at least one selected from sodium hydroxide solution and potassium hydroxide solution; the heating and stirring time is 10-13 h under the temperature condition of 50-60 ℃, for example, the temperature can be 50 ℃, 52 ℃, 55 ℃ and 60 ℃, and the time can be 10h, 11h, 12h, 13h and the like. Under the condition, the nano silver wire can be better hydroxylated.
In one embodiment, the carboxyl-containing cellulose may be selected from one or a mixture of carboxyl nanocellulose or other carboxyl-containing bacterial cellulose. For example, carboxyl nanocellulose can be prepared by a one-step oxidation method using ammonium persulfate, and specifically, the carboxyl nanocellulose is esterified by a one-pot method using cellulose as a raw material and ammonium persulfate as an oxidizing agent.
In one embodiment, the step of subjecting the hydroxylated silver nanowires to an esterification reaction with a carboxyl-containing cellulose, such as a carboxyl nanocellulose, in an alcohol solvent comprises: dispersing the hydroxylated nano silver wire in a first alcohol solvent to obtain a nano silver wire dispersion liquid; dispersing cellulose containing carboxyl in a second alcohol solvent to obtain a cellulose dispersion liquid; mixing the nano silver wire dispersion liquid and the cellulose dispersion liquid to obtain a mixed liquid, and then carrying out hydrothermal treatment on the mixed liquid. In an alcohol solvent, the esterification reaction is promoted by hydrothermal conditions, and hydroxyl on the surface of the silver nanowire can better react with carboxyl on the surface of cellulose.
In one embodiment, after the silver nanowire dispersion and the cellulose dispersion are mixed to obtain a mixed solution, the mixed solution is subjected to a hydrothermal treatment, wherein: the dehydrating agent is added into the mixed solution. For example, sodium hypophosphite (NaPH) with a strong dehydrating agent is added 2 O 2 ) This can promote the esterification reaction better. As shown in FIG. 2, the carboxyl on the surface of the cellulose and the hydroxyl on the surface of the nano-silver wire which is heat treated by the sodium hydroxide solution are in the dehydrating agent NaPH 2 O 2 And dehydrating and condensing under the action of the catalyst to obtain the composite material with better stability.
Specifically, the alcohol solvent used for the esterification reaction between the hydroxylated silver nanowires and the cellulose containing carboxyl groups in the alcohol solvent includes a first alcohol solvent and a second alcohol solvent, which may be the same or different. For example, methanol, ethanol and propanol may be the same or different. Ethanol is preferred.
Further, the temperature of the hydrothermal treatment is 130-150 ℃, such as 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃ and the like, and the time is 25-35 min, such as 25min, 27min, 30min, 35min and the like. The esterification reaction can be sufficiently performed under such conditions.
Further, dispersing the hydroxylated nano silver wires in a nano silver wire dispersion liquid obtained by a first alcohol solvent, wherein the mass concentration of the nano silver wires is 4-6 mg/ml, such as 4mg/ml, 4.5mg/ml, 5mg/ml, 5.5mg/ml and 6 mg/ml; dispersing cellulose containing carboxyl in a second alcohol solvent to obtain a cellulose dispersion liquid, wherein the mass concentration of the cellulose is 0.1-0.3 mg/ml, such as 0.1mg/ml, 0.15mg/ml, 0.2mg/ml, 0.25mg/ml and 0.3 mg/ml; and in the mixed solution obtained by mixing the silver nano-wire and the cellulose, the mass ratio of the silver nano-wire to the cellulose is 1: 1.5-2.5, such as 1: 1.5,1: 2,1: 2.2,1: 2.5. under the conditions, the nano silver wire and the cellulose are fully combined, so that the comprehensive effect of the conductive stability and the self-repairing capability of the obtained composite material is optimal.
Specifically, the esterification reaction product solution obtained by the esterification reaction contains the composite material, and the esterification reaction product solution is sequentially subjected to filtration treatment and drying treatment, so that the dried composite material can be extracted.
In one embodiment, the filtration process is vacuum filtration. And (4) performing suction filtration to obtain a product which can be a composite material film, and further drying to obtain the composite material solid film. And the composite material film is a cellulose film containing nano silver wires, has excellent conductive stability and self-repairing capability, and can be used as a conductive film in a flexible electronic device.
In one embodiment, the drying step includes vacuum drying at 30-36 deg.C, specifically 30 deg.C, 32 deg.C, 35 deg.C, 36 deg.C, etc. So that the alcohol solvent can be more volatile.
The embodiment of the application also provides a composite material, and the composite material is prepared by the preparation method of the embodiment of the application. Based on the characteristics of the preparation method of the composite material, the composite material disclosed by the embodiment of the application has excellent conductive stability and self-repairing capability, and has a good application prospect. All the optional schemes of the preparation method of the composite material can be used in the composite material, so that the composite material has all the advantages of the preparation method provided by the above embodiment, and the details are not repeated herein.
The embodiment of the application also provides an application of the composite material in a flexible electronic device. The composite material prepared by the preparation method based on the embodiment of the application has the characteristics of being used as a conductive film and well applied to flexible electronic devices.
The preparation method of the composite material based on the embodiment of the application is simple and easy to operate, low in cost and capable of realizing large-scale production, and the composite material prepared by the preparation method can be used as a cellulose paper-based film containing nano silver wires, has excellent self-repairing performance and good conductive stability, has the advantage of high self-definition, and can be used for preparing an electrical self-repairing material with high mechanical strength as required.
The following description will be given with reference to specific examples.
Example 1
The preparation method of the composite material comprises the following steps:
(1) preparing silver nanowires:
preparing a mixed solution: weighing 0.2g of silver nitrate, dissolving the silver nitrate in 20mL of ethylene glycol, uniformly stirring, adding 0.4g of polyvinylpyrrolidone (molecular weight of 58000) after the silver nitrate is dissolved, and uniformly stirring to obtain a mixed solution;
and (3) synthesis of the nanowire: weighing copper chloride dihydrate, dissolving the copper chloride dihydrate in ethylene glycol, and preparing a copper chloride solution with the concentration of 4 mM; adding 20mL of ethylene glycol into a 100mL three-neck round bottom flask, putting the mixture into an oil bath pot, heating the mixture to 160 ℃, keeping the temperature for 1 hour, then adding 2-4 mL of prepared copper chloride solution, and continuing heating and stirring for 15 min; slowly dripping the mixed solution containing the nitrate and the polyvinylpyrrolidone into a round-bottom flask by using a constant-pressure separating funnel, wherein the process takes 30 min; maintaining the temperature of the system and stirring in the dropping process; after the dropwise addition is finished, continuously heating and stirring for 30min for reaction; and cooling, centrifuging and washing the suspension obtained after the reaction is finished, and re-dispersing the suspension into ethanol to obtain the ethanol dispersion liquid of the nano silver wires.
(2) Modification of silver nanowires
Placing the obtained nano silver wire in a sodium hydroxide solution, heating and stirring at 50 ℃ for 12h to obtain a hydroxylated nano silver wire; then, the nanometer silver wire is centrifuged, washed and re-dispersed into ethanol to obtain hydroxylated nanometer silver wire dispersion liquid (the mass concentration is 5 mg/ml).
(3) Synthesis of composite materials
The carboxyl nano-cellulose is prepared by taking cellulose as a raw material and utilizing an ammonium persulfate one-step oxidation method. Dispersing appropriate amount of carboxyl nanocellulose into ethanol, and using milkThe chemical machine is uniformly dispersed; to obtain carboxyl nano-cellulose solution (mass concentration is 0.2 mg/ml). The carboxyl nanocellulose solution and the hydroxylated nano-silver wire dispersion liquid obtained above (wherein, the carboxyl nanocellulose is 10mg, and the hydroxylated nano-silver wire is 5mg) were mixed and dispersed for 3 hours by using an emulsifying machine, and the mixture was further stirred and dispersed for 12 hours to be uniformly dispersed in the liquid, so that a mixed liquid was obtained. Transferring the obtained mixed solution into a reaction kettle, and adding NaPH 2 O 2 Then, the reaction was carried out by hydrothermal heating to 140 ℃ in a closed atmosphere for 30 minutes. After the reaction, the reaction mixture was filtered by a vacuum filtration apparatus, and the obtained solid was collected, dried for 12 hours at 35 ℃ in a vacuum oven, and then compressed into a composite film having a thickness of 80 μm, as shown in fig. 3.
Example 2
The preparation method of the composite material comprises the following steps:
(1) preparing silver nanowires:
the same as in example 1.
(2) Modification of silver nanowires
Placing the obtained nano silver wire in a sodium hydroxide solution, heating and stirring at 60 ℃ for 13h to obtain a hydroxylated nano silver wire; then, the solution is centrifuged, washed and re-dispersed in ethanol to obtain hydroxylated nano silver wire dispersion liquid (the mass concentration is 6 mg/ml).
(3) Synthesis of composite materials
The carboxyl nano-cellulose is prepared by taking cellulose as a raw material and utilizing an ammonium persulfate one-step oxidation method. Taking a proper amount of carboxyl nano cellulose to disperse into ethanol, and using an emulsifying machine to disperse uniformly; to obtain carboxyl nano-cellulose solution (mass concentration is 0.1 mg/ml). The carboxyl nanocellulose solution and the hydroxylated nano silver wire dispersion liquid obtained above (wherein, the carboxyl nanocellulose is 15mg, and the hydroxylated nano silver wire is 6mg) are mixed and dispersed for 4 hours by using an emulsifying machine, and the mixture is continuously stirred and dispersed for 14 hours to be uniformly dispersed in the liquid, so that a mixed liquid is obtained. Transferring the obtained mixed solution into a reaction kettle, sealing, carrying out hydrothermal heating to 150 ℃, and reacting for 30 minutes. After the reaction, the reaction product was filtered by a vacuum filtration apparatus, and the obtained solid was collected, dried for 12 hours at 35 ℃ in a vacuum oven, and then compressed into a composite film having a thickness of 90 μm.
Comparative example 1
The preparation method of the composite material comprises the following steps:
cellulose is not carboxylated, and the nano silver wires are not hydroxylated, and the cellulose and the nano silver wires are directly and fully dispersed by ethanol to obtain a mixed solution (wherein, the cellulose is 10mg, and the nano silver wires are 5 mg). The obtained mixed solution was filtered with a vacuum filtration apparatus, and the obtained solid was collected, dried for 12 hours under vacuum at 35 ℃ using a vacuum drying oven, and then compressed into a composite film of 80 μm thickness.
Comparative example 2
The preparation method of the composite material comprises the following steps:
cellulose is not carboxylated and the nano silver wire is not hydroxylated, and the cellulose and the nano silver wire are directly and fully dispersed by ethanol to obtain a mixed solution (wherein the cellulose is 15mg, and the nano silver wire is 6 mg). The obtained mixed solution was filtered with a vacuum filtration apparatus, and the obtained solid was collected, dried for 12 hours under vacuum at 35 ℃ using a vacuum drying oven, and then compressed into a composite material film having a thickness of 90 μm.
Performance testing
The composite films prepared in the above examples and comparative examples were measured by a resistance tester: after repeated bending at the same position for a plurality of times (50 times and 100 times), the resistance increase range is shown in table 1.
TABLE 1
| Item | 50 times bending resistance increase range | 100 times bending resistance increase range |
| Example 1 | 3.4％ | 7％ |
| Example 2 | 3.8％ | 8.1％ |
| Comparative example 1 | 10％ | 19％ |
| Comparative example 2 | 11％ | 20％ |
As can be seen from table 1 above, the composite material prepared in the examples of the present application has better conductive stability.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The preparation method of the composite material is characterized by comprising the following steps:
providing a nano silver wire;
carrying out alkali heating treatment on the nano silver wire to obtain a hydroxylated nano silver wire;
carrying out esterification reaction on the hydroxylated nano silver wire and cellulose containing carboxyl in an alcohol solvent to obtain an esterification reaction product solution;
and sequentially filtering and drying the esterification reaction product solution to obtain the composite material.
2. The method of claim 1, wherein the step of subjecting the silver nanowires to an alkali heat treatment comprises: and (3) placing the nano silver wire in an alkali solution, and then heating and stirring at the temperature of 50-60 ℃.
3. The method according to claim 2, wherein the alkali solution is at least one selected from a sodium hydroxide solution and a potassium hydroxide solution; and/or the presence of a gas in the gas,
the heating and stirring time is 10-13 h.
4. The method of claim 1, wherein the step of subjecting the hydroxylated silver nanowires to an esterification reaction with a cellulose containing carboxyl groups in an alcohol solvent comprises:
dispersing the hydroxylated nano silver wire in a first alcohol solvent to obtain a nano silver wire dispersion liquid;
dispersing the cellulose containing carboxyl in a second alcohol solvent to obtain a cellulose dispersion liquid;
and mixing the nano silver wire dispersion liquid and the cellulose dispersion liquid to obtain a mixed liquid, and then carrying out hydrothermal treatment on the mixed liquid.
5. The preparation method according to claim 4, wherein the temperature of the hydrothermal treatment is 130 to 150 ℃ and the time is 25 to 35 min; and/or the presence of a gas in the gas,
the step of subjecting the mixed solution to hydrothermal treatment comprises: and a dehydrating agent is added into the mixed solution.
6. The method according to claim 4, wherein the mass concentration of the nano-silver wire dispersion is 4 to 6mg/ml, and the mass concentration of the cellulose dispersion is 0.1 to 0.3 mg/ml; and/or the presence of a gas in the gas,
in the mixed solution, the mass ratio of the nano silver wires to the cellulose is 1: 1.5 to 2.5.
7. The production method according to any one of claims 1 to 6, wherein the filtration treatment is vacuum filtration; and/or the presence of a gas in the gas,
the drying treatment step comprises vacuum drying at the temperature of 30-36 ℃.
8. The method of any one of claims 1 to 6, wherein the method of preparing the silver nanowires comprises:
preparing a polyalcohol solution containing silver salt and polyvinylpyrrolidone;
and dropwise adding the polyhydric alcohol solution into a polyhydric alcohol base solution containing copper chloride at 140-160 ℃, and keeping the temperature for 30-120 min.
9. A composite material produced by the production method according to any one of claims 1 to 8.
10. Use of the composite material of claim 9 in a flexible electronic device.
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