阅读说明：本技术 一种金属纳米线结构化网络搭接方法及其应用 (metal nanowire structured network lapping method and application thereof ) 是由 赵祖珍 孙兵妹 方春晖 邓锦鸿 于 2019-09-20 设计创作，主要内容包括：本发明涉及金属纳米线领域,具体涉及一种金属纳米线结构化网络搭接方法及其应用。所述金属纳米线结构化网络搭接方法包括如下步骤：(1)用分散剂处理金属纳米线,得混合物A；(2)向所述混合物A中加入相同的金属离子混合均匀,得混合物B；(3)再向所述混合物B加入还原剂进行还原反应。通过在金属纳米线中引入金属盐,使得金属纳米线表面生长金属颗粒。带有金属颗粒的金属纳米线涂覆在基材上时,由于静电吸附原理,邻近的金属纳米线间的距离大大减小,降低了电阻。(the invention relates to the field of metal nanowires, in particular to a metal nanowire structured network lapping method and application thereof. The metal nanowire structured network lapping method comprises the following steps: (1) treating the metal nanowire by using a dispersing agent to obtain a mixture A; (2) adding the same metal ions into the mixture A and uniformly mixing to obtain a mixture B; (3) and adding a reducing agent into the mixture B to perform reduction reaction. And introducing a metal salt into the metal nanowire to enable metal particles to grow on the surface of the metal nanowire. When the metal nano-wire with the metal particles is coated on the base material, the distance between the adjacent metal nano-wires is greatly reduced due to the electrostatic adsorption principle, and the resistance is reduced.)

1. a metal nanowire structured network lapping method is characterized by comprising the following steps: (1) treating the metal nanowire by using a dispersing agent to obtain a mixture A; (2) adding the same metal ions into the mixture A and uniformly mixing to obtain a mixture B; (3) and adding a reducing agent into the mixture B to perform reduction reaction.

2. The method according to claim 1, wherein the mass ratio of the dispersing agent to the metal nanowires in the step (1) is (0.01-0.3):1, and the treatment method comprises the steps of uniformly mixing the dispersing agent and the metal nanowires, stirring for reaction and then carrying out centrifugal purification.

3. The method of claim 2, wherein the dispersant is a polymer and its derivatives that are negatively charged when dissolved in water.

4. The method according to claim 1, wherein the mass ratio of the metal ions to the metal nanowires in step (2) is (0.1-1): 1.

5. The method according to claim 1, wherein the mass ratio of the reducing agent to the metal nanowires in step (3) (0.2-2): 1.

6. the method of claim 5, wherein the reducing agent comprises one or more of sodium citrate, disodium citrate, trisodium citrate, sodium hypophosphite, hydroxylamine hydrochloride, glucose, ascorbic acid, edetate, ethylene glycol, sodium borohydride.

7. The method of claim 1, wherein the nano-metal wires comprise one or more of silver, copper, gold, iron, tin, titanium, platinum, palladium, nickel, cobalt; the metal ions comprise one or more of silver ions, copper ions, gold ions, iron ions, tin ions, titanium ions, platinum ions, palladium ions, nickel ions and cobalt ions.

8. metal nanowires with a structured network prepared by applying the method according to any one of claims 1 to 7.

9. The metal nanowire is characterized by comprising a metal nanowire body and metal particles which are connected with the metal nanowire body and have the same elements, wherein a network structure is formed by overlapping part or all of the metal nanowires through the metal particles.

10. A conductive film, comprising a substrate and a conductive layer coated on the substrate, wherein the conductive layer comprises metal nanowires and an auxiliary agent, the metal nanowires are the metal nanowires of claim 9, and the impedance value of the conductive film is not higher than 62 Ω/cm 2.

Technical Field

The invention relates to the field of metal nanowires, in particular to a metal nanowire structured network lapping method and application thereof.

Background

The metal nanowire is considered as an optimal material for preparing a new generation of transparent conductive electrode due to excellent electrical properties, optical properties and mechanical flexibility. However, the conductive network formed by the metal nanowires has large contact resistance and weak acting force with the substrate, and limits the performance limit of the transparent conductive film and the application of the transparent conductive film in the field of electric films. The metal nanowire structured network lapping refers to reducing or decreasing the distance between the nanowires, so that the adjacent metal nanowires are contacted more tightly, and the resistance of the metal nanowires in application is reduced or decreased.

Chinese patent publication No. CN104685577A discloses a metal nanostructured network and a transparent conductive material. This patent delivers metal nanowires deposited on a substrate with a halide solution or hydrogen halide vapor to form a structured network of nanowires in a core-shell structure, where the shell is the metal halide and the core is the metal nanowires. However, in industrial production, the method needs to be completed under steam conditions, and the steam conditions are high and difficult to operate, so that the conductive film is low in production efficiency and high in energy consumption cost.

Disclosure of Invention

In order to solve the above problems, the present invention provides a metal nanowire structured network overlapping method and application thereof.

a metal nanowire structured network lapping method comprises the following steps: (1) treating the metal nanowire by using a dispersing agent to obtain a mixture A; (2) adding the same metal ions into the mixture A and uniformly mixing to obtain a mixture B; (3) and adding a reducing agent into the mixture B to perform reduction reaction.

Further, the mass ratio of the dispersing agent to the metal nanowires in the step (1) is (0.01-0.3):1, and the processing method comprises the steps of uniformly mixing the dispersing agent and the metal nanowires, stirring for reaction for 0.5-3h, and then carrying out centrifugal purification to obtain the modified metal nanowires, namely a mixture A.

furthermore, the dispersing agent is a polymer with negative electricity after being dissolved in water and a derivative thereof. The negatively charged dispersing agent modifies the metal nanowire to enable the surface of the metal nanowire to be negatively charged, so that the agglomeration phenomenon of the metal nanowire can be improved and the dispersibility of the metal nanowire is optimized, and the negatively charged metal nanowire on the surface can absorb positively charged metal ions to enable metal particles to grow on the surface of the metal nanowire.

Furthermore, the dispersant comprises one or more of polyethylene acid and derivatives thereof, polyacrylate, polymethacrylate, salts of maleic anhydride-styrene copolymer, methylcellulose, carboxymethyl cellulose, ethyl cellulose, polymers of 3, 4-ethylenedioxythiophene monomers, polystyrene sulfonate and propyl cellulose.

Further, the mass ratio of the metal ions to the metal nanowires in the step (2) is (0.1-1): 1. The modification method comprises mixing the two, stirring for reaction for 0.5-3h, and centrifuging for purification to obtain mixture B.

Further, in the step (3), the mass ratio (0.2-2) of the reducing agent to the metal nanowire is 1, and the reducing method comprises the steps of adding the reducing agent into the mixture B, uniformly mixing, and reacting at 20-60 ℃ for 0.5-2h to obtain the metal nanowire with the structured network. The reducing agent can reduce metal ions attached to the surface of the metal nanowire, so that the metal ions are reduced to form nucleus and grow.

Still further, the reducing agent includes one or more of sodium citrate, disodium citrate, trisodium citrate, sodium hypophosphite, hydroxylamine hydrochloride, glucose, ascorbic acid, edetate, ethylene glycol, sodium borohydride.

Further, the nano metal wire comprises one or more of silver, copper, gold, iron, tin, titanium, platinum, palladium, nickel and cobalt; the metal ions comprise one or more of silver ions, copper ions, gold ions, iron ions, tin ions, titanium ions, platinum ions, palladium ions, nickel ions and cobalt ions.

Furthermore, the length of the nano metal wire is 15-40um, and the diameter of the nano metal wire is 15-50 nm.

A metal nanowire with a structured network prepared using the method described above.

the metal nanowire comprises a metal nanowire body and metal particles which are connected with the metal nanowire body and have the same elements, wherein a network structure is formed by overlapping part or all of the metal nanowires through the metal particles.

The conductive film comprises a substrate and a conductive layer coated on the substrate, wherein the conductive layer comprises a metal nanowire and an auxiliary agent, the metal nanowire comprises a metal nanowire body and metal particles with the same elements, and the impedance value of the conductive film is not higher than 62 omega/cm 2

The invention has the beneficial effects that: and introducing metal ions into the metal nanowires to enable metal particles to grow on the surfaces of the metal nanowires. When the metal nano-wire with the metal particles is coated on the base material, the distance between the adjacent metal nano-wires is greatly reduced due to the electrostatic adsorption principle, and the resistance is reduced; more importantly, the particles on the metal nanowires are connected with the adjacent metal nanowires like a bridge, so that the conductive capacity is further improved. The method realizes that the resistance of the metal nanowire is reduced from thousands of ohms per square before processing to dozens of ohms per square after processing. The metal particles and the metal nanowires can be composed of the same metal, and the metal particles and the metal nanowires can also not be composed of the same metal; the metal particles may be composed of one metal or several metals.

Specifically, after metal particles grow on the metal nanowires, the negatively charged dispersant on the metal nanowires attracts not only the metal particles growing thereon, but also the metal particles on the adjacent metal nanowires; similarly, the metal particles on the metal nanowires are attracted by the negatively charged dispersants on the adjacent metal nanowires, and just because of the attraction, the distance between two or more silver nanowires when in contact with each other is greatly reduced, so that the resistance of the silver nanowires is greatly reduced. In addition, the reason for causing the resistance between the metal nanowires to be larger also includes that the longitudinal distance of the metal nanowires is longer, namely, one end of one nano metal wire is farther away from one end of the other adjacent metal nanowire, and the impedance value is still large.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a silver nanowire with a structured network prepared in example 1;

FIG. 2 is a silver nanowire with a structured network prepared in example 2;

Fig. 3 is a silver nanowire with a structured network prepared in example 3.

Fig. 4 is a simulation diagram of the lapping mode of the silver nanowires with the structured network of the present invention, wherein a is the connection of one end of a metal nanowire with one end of another metal nanowire, B is the connection of one end of a metal nanowire with another metal nanowire, and C is the "wire-line" connection of two metal nanowires.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

a metal nanowire structured network lapping method is characterized by comprising the following steps: (1) treating the metal nanowire by using a dispersing agent to obtain a mixture A; (2) adding metal salt into the mixture A and uniformly mixing to obtain a mixture B; (3) and adding a reducing agent into the mixture B to perform reduction reaction.