阅读说明：本技术 一种可拉伸高导电性材料的制备方法及其应用 (Preparation method and application of stretchable high-conductivity material ) 是由 不公告发明人 于 2021-09-09 设计创作，主要内容包括：本发明提供了一种可拉伸高导电性材料的制备方法,将纳米银粉、石墨烯衍生物和液态金属按照质量比为(0.1-0.28)：(0.05-0.1)：1混合,球磨后获得纳米银粉-石墨烯-液态金属复合导电材料。该复合导电材料可采用丝网印刷的方式在刚性或柔性基底表面印制高导电性电子电路。该方法制备简单、可批量化制备,且无需额外处理,并可满足可穿戴电子、电子皮肤、智能传感、机器人等领域的应用需求。(The invention provides a preparation method of a stretchable high-conductivity material, which comprises the following steps of mixing nano silver powder, a graphene derivative and liquid metal according to a mass ratio of (0.1-0.28): (0.05-0.1): 1, mixing and ball-milling to obtain the nano silver powder-graphene-liquid metal composite conductive material. The composite conductive material can be used for printing a high-conductivity electronic circuit on the surface of a rigid or flexible substrate by adopting a screen printing mode. The method is simple to prepare, can be prepared in batch, does not need additional treatment, and can meet the application requirements in the fields of wearable electronics, electronic skin, intelligent sensing, robots and the like.)

1. A preparation method of a stretchable high-conductivity material is characterized in that nano silver powder, a graphene derivative and liquid metal are mixed according to a mass ratio of (0.1-0.28): (0.05-0.1): 1, mixing, and performing ball milling to obtain the nano silver powder-graphene-liquid metal composite conductive material, wherein the ball milling rotation speed is 500 plus 1,000 rpm, the ball milling time is 3-6 h, and vacuumizing and argon filling are performed once every 1 h before and during the ball milling.

2. The method for preparing stretchable highly conductive material according to claim 1, wherein the silver solid content of the silver nanoparticles is greater than 99% and the particle size is less than 150 nm.

3. The method for preparing a stretchable highly conductive material as claimed In claim 1, wherein the liquid metal is one or more of Ga-In and Ga-In-Zn alloy; the Ga-In alloy contains 65-95 parts by mass of metal gallium and 5-35 parts by mass of metal indium; the Ga-In-Zn alloy contains 65-95 parts by mass of metal gallium, 5-35 parts by mass of metal indium and 5-20 parts by weight of metal zinc.

4. The method for preparing the stretchable high-conductivity elastomer according to claim 1, wherein the graphene derivative comprises one or more of graphene oxide, reduced graphene oxide, nitrogen-doped graphene, sulfur-doped graphene and nitrogen-sulfur co-doped graphene.

5. The method as claimed in claim 1, wherein the silver nanoparticle powder-graphene-liquid metal composite conductive material is a high viscosity composite semi-solid material with a viscosity of 8,000-12,000 cp.

6. The use of the stretchable high-conductivity material prepared by the method according to claim 1, wherein the electronic circuit is prepared by using the silver nanoparticle powder-graphene-liquid metal composite conductive material on the surface of a rigid substrate or a flexible substrate by means of screen printing or slit coating.

7. The use according to claim 6, wherein the rigid substrate is a PCB board, an alumina ceramic board, an aluminum nitride ceramic board, an aluminum substrate or a copper substrate.

8. Use according to claim 6, wherein the flexible substrate is PET, PVC, PI, PEN, Teslin or photographic paper.

9. Use according to claim 6, wherein the electronic circuit prepared on a flexible substrate has a stretchability of from 200% to 1,000%.

10. The use of claim 6, wherein said electronic circuit is used in wearable electronics, electronic skin, smart sensors and flexible robots.

Technical Field

The invention relates to the technical field of electronic material preparation and device processing, in particular to a preparation method and an application mode of a stretchable high-conductivity material.

Background

In recent years, electronic information technology has been developed, and electronic devices have been miniaturized and light-weighted. Among them, the rise of wearable devices will certainly push flexible electronic devices to develop into one of the mainstream directions in the electronic field. However, this critical technical problem is to be solved here: (1) flexible substrates, the conventional ITO (indium tin oxide) material, have dominated the entire industry for almost a long time due to its characteristics of transparency, conductivity, etc. However, the application and development of ITO materials are limited by their high cost, high impedance, poor light transmission, poor flexibility, and other problems. (2) The electrical conductivity and stretchability of the conductive material. At present, electronic circuits printed by adopting a screen printing or ink-jet printing mode mainly adopt high-elasticity-modulus and high-conductivity particles such as nano silver powder, graphene, carbon nanotubes and the like as a conductive medium. The existence of these two types of problems limits the further development of flexible electronic technology.

However, the preparation of conductive inks with metals (copper, silver, etc.) and carbon-based (graphene, carbon nanotubes, etc.) as conductive media has the following disadvantages: high elastic modulus, low elongation at break and no good stretchability. Therefore, the development of a novel conductive material with good stretchability and conductivity is a vital force for promoting the development of flexible electronic technology. In recent years, room temperature liquid metal materials represented by gallium and gallium-based alloys have excellent electrical properties over conventional electronic materials, and are expected to be applied to printing high-performance electronic circuits. However, the huge surface energy of the liquid metal and the spontaneous formation of an insulating oxide film on the surface of the liquid metal limit the printing effect and the electric conductivity of the liquid metal on various substrates.

Therefore, the preparation method of the stretchable high-conductivity material is characterized in that the nano silver powder, the graphene derivative and the liquid metal are compounded, the stretchable high-conductivity composite conductive material can be obtained through a simple ball milling mode, and the composite conductive material is used for printing a high-conductivity electronic circuit. Meanwhile, the method is simple to operate, can be used for batch preparation, and does not need an additional treatment process. In addition, the stretchable and high-conductivity electronic circuit prepared by the method can meet the application requirements of civil fields such as wearable electronics, electronic skin, intelligent sensing and robots.

Disclosure of Invention

Based on the technical problems in the background art, the invention aims to provide a preparation method of a stretchable high-conductivity material, and the high-conductivity composite conductive material can be obtained through a simple ball milling mode. The composite conductive material is a high-viscosity semi-solid state, and the viscosity of the composite conductive material is suitable for printing an electronic circuit on the surface of a rigid or flexible substrate by adopting a screen printing mode. The method is simple to operate, can be used for batch preparation, and does not need an additional treatment process. In addition, the high-conductivity electronic circuit prepared by the method can meet the application requirements of civil fields such as wearable electronics, electronic skin, intelligent sensing and robots. The specific technical scheme is as follows:

the preparation method comprises the following steps of (1) mixing nano silver powder, graphene derivatives and liquid metal according to a mass ratio of (0.1-0.28): (0.05-0.1): 1, mixing, and performing ball milling to obtain the nano silver powder-graphene-liquid metal composite conductive material, wherein the ball milling rotation speed is 500 plus 1,000 rpm, the ball milling time is 3-6 h, and vacuumizing and argon filling are performed once every 1 h before and during the ball milling. Organic gas is generated in the preparation process of the nano silver powder-graphene-liquid metal composite conductive material and needs to be removed in time to avoid oxidizing liquid metal;

the solid content of silver in the nano silver powder is more than 99%, and the particle size is less than 150 nm; the organic ligand on the surface of the nano silver powder volatilizes in the high-speed stirring process and oxidizes liquid metal, so that the conductivity of the nano silver powder-graphene-liquid metal composite conductive material is reduced, and therefore the nano silver powder with high silver solid content is required to be used;

the liquid metal is one or more of Ga-In and Ga-In-Zn alloy. The Ga-In alloy contains 65-95 parts by mass of metal gallium and 5-35 parts by mass of metal indium. The Ga-In-Zn alloy contains 65-95 parts by mass of metal gallium, 5-35 parts by mass of metal indium and 5-20 parts by weight of metal zinc.

The graphene derivative comprises one or more of graphene oxide, reduced graphene oxide, nitrogen-doped graphene, sulfur-doped graphene and nitrogen-sulfur co-doped graphene.

The nano silver powder-graphene-liquid metal composite conductive material is a high-viscosity composite semi-solid material, and the viscosity is 8,000-12,000 cp.

The application mode of the stretchable high-conductivity material is that the nano silver powder-graphene-liquid metal composite conductive material is used for preparing an electronic circuit on the surface of a rigid substrate or a flexible substrate in a screen printing or slit coating mode.

The rigid substrate is a PCB (printed Circuit Board), an alumina ceramic plate, an aluminum nitride ceramic plate, an aluminum substrate or a copper substrate.

The flexible substrate is PET, PVC, PI, PEN, Teslin or photographic paper.

The electronic circuit prepared on the flexible substrate has the stretching rate of 200-1,000%.

The stretchable and high-conductivity electronic circuit can meet the application requirements of wearable equipment, electronic skin, intelligent sensing and flexible robots.

The invention has the beneficial effects that: the preparation method of the stretchable high-conductivity composite conductive material is designed and prepared, and the high-conductivity composite conductive material can be obtained through a simple ball milling mode. The composite conductive material is a high-viscosity semi-solid state, and the viscosity of the composite conductive material is suitable for printing an electronic circuit on the surface of a rigid or flexible substrate by adopting a screen printing mode. The method is simple to operate, can be used for batch preparation, and does not need an additional treatment process. In addition, the high-conductivity electronic circuit prepared by the method can meet the application requirements of civil fields such as wearable electronics, electronic skin, intelligent sensing and robots.

Drawings

Fig. 1 is an SEM image of the nano silver powder-graphene-liquid metal semi-solid composite conductive material in example 1 of the present invention;

fig. 2 is a SEM image of a liquid metal without using a nano silver powder and a graphene derivative in comparative example 1 of the present invention.

Detailed Description

The technical solution of the present invention will be described clearly and completely with reference to the following embodiments and the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

In the prior art, the problems of poor stretchability of an electronic circuit printed by the nano silver powder, poor conductivity of graphene, poor adhesion of liquid metal, easy oxidation of the surface and the like limit the application of the nano silver powder in the field of flexible electronics. In order to solve the problems, the invention provides a preparation method of a stretchable and high-conductivity material, and the high-conductivity composite conductive material can be obtained by a simple ball milling mode. The composite conductive material is a high-viscosity semi-solid state, and the viscosity of the composite conductive material is suitable for printing an electronic circuit on the surface of a rigid or flexible substrate by adopting a screen printing mode. The method is simple to operate, can be used for batch preparation, and does not need an additional treatment process. In addition, the high-conductivity electronic circuit prepared by the method can meet the application requirements of civil fields such as wearable electronics, electronic skin, intelligent sensing and robots.

Example 1

A preparation method of a stretchable and high-conductivity material comprises the following steps:

nano silver powder, nitrogen-sulfur co-doped graphene and liquid metal Ga-In alloy according to the mass ratio of 0.1: 0.08: 1, and ball-milling to obtain the silver powder-graphene-liquid metal composite conductive material, wherein fig. 1 is an SEM image of the silver powder-graphene-liquid metal composite conductive material in example 1 of the present invention.

Wherein the ball milling speed is 500 rpm, the ball milling time is 6 h, and before ball milling and in the ball milling process, the vacuum pumping and argon filling are carried out once every 1 h.

The solid content of silver in the nano silver powder is 99.95%, and the particle size is 50 nm.

The Ga-In alloy contains 65 parts by mass of metal gallium and 35 parts by mass of metal indium;

the nano silver powder-graphene-liquid metal composite conductive material is a high-viscosity composite semi-solid material, and the viscosity is 8,500 cp.

The nano silver powder-graphene-liquid metal composite conductive material is used for printing a high-conductivity electronic circuit on the surface of a PCB (printed Circuit Board) by adopting a screen printing mode.

The high-conductivity electronic circuit can meet the application requirements of wearable electronics, electronic skins, intelligent sensing and robots.

Example 2

A preparation method of a stretchable and high-conductivity material comprises the following steps:

mixing nano silver powder, reduced graphene oxide and liquid metal Ga-In-Zn alloy according to the mass ratio of 0.28: 0.1: 1, mixing, and performing ball milling to obtain the nano silver powder-graphene-liquid metal composite conductive material, wherein the ball milling rotation speed is 1,000 rpm, the ball milling time is 4 hours, and vacuumizing and argon filling are performed once every 1 hour before and during the ball milling.

The solid content of silver in the nano silver powder is 99.7%, and the particle size is 120 nm.

The Ga-In-Zn alloy contains 65 parts by mass of metal gallium, 35 parts by mass of metal indium and 5 parts by weight of metal zinc.

The nano silver powder-graphene-liquid metal composite conductive material is a high-viscosity composite semi-solid material, and the viscosity is 12,000 cp.

The nano silver powder-graphene-liquid metal composite conductive material is used for printing a high-conductivity electronic circuit on the surface of PET in a screen printing mode, and the prepared flexible electronic circuit has the stretchability of 1,000%.

The high-conductivity electronic circuit can meet the application requirements of wearable electronics, electronic skins, intelligent sensing and robots.

Example 3

A preparation method of a stretchable and high-conductivity material comprises the following steps:

mixing nano silver powder, nitrogen-doped graphene and liquid metal Ga-In alloy according to the mass ratio of 0.28: 0.05: 1, mixing, and performing ball milling to obtain the nano silver powder-graphene-liquid metal composite conductive material, wherein the ball milling rotation speed is 600 rpm, the ball milling time is 3 hours, and vacuumizing and argon filling are performed once every 1 hour before and during the ball milling.

The solid content of silver in the nano silver powder is 99.95%, and the particle size is 50 nm.

The Ga-In alloy contains 95 parts by mass of metal gallium and 5 parts by mass of metal indium;

the nano silver powder-graphene-liquid metal composite conductive material is a high-viscosity composite semi-solid material, and the viscosity is 11,000 cp.

The nano silver powder-graphene-liquid metal composite conductive material is used for printing a high-conductivity electronic circuit on the surface of the aluminum nitride ceramic plate in a screen printing mode.

The high-conductivity electronic circuit can meet the application requirements of wearable electronics, electronic skins, intelligent sensing and robots.

In another embodiment, the aluminum nitride ceramic plate may be replaced with an aluminum oxide ceramic plate, an aluminum substrate, or a copper substrate.

Example 4

A preparation method of a stretchable and high-conductivity material comprises the following steps:

mixing nano silver powder, sulfur-doped graphene and liquid metal Ga-In alloy according to a mass ratio of 0.1: 0.1: 1, mixing, and performing ball milling to obtain the nano silver powder-graphene-liquid metal composite conductive material, wherein the ball milling rotation speed is 800 rpm, the ball milling time is 5 hours, and vacuumizing and argon filling are performed once every 1 hour before and during the ball milling.

The solid content of silver in the nano silver powder is 99.5%, and the particle size is 100 nm.

The Ga-In-Zn alloy contains 80 parts by mass of metal gallium, 5 parts by mass of metal indium and 20 parts by weight of metal zinc.

The nano silver powder-graphene-liquid metal composite conductive material is a high-viscosity composite semi-solid material, and the viscosity is 9,500 cp.

The nano silver powder-graphene-liquid metal composite conductive material is used for printing a high-conductivity electronic circuit on the PVC surface in a screen printing mode, and the prepared flexible electronic circuit has the stretchability of 950%.

The high-conductivity electronic circuit can meet the application requirements of wearable electronics, electronic skins, intelligent sensing and robots.

In another embodiment the PVC may be replaced with PI, PEN, Teslin or photographic paper.

Comparative example 1

The technical scheme of the embodiment 1 is changed as follows: the prepared electronic circuit has poor conductivity and adhesiveness because nano silver powder or graphene compounded liquid metal is not used. Fig. 2 is a SEM image of a liquid metal without using a nano silver powder and a graphene derivative in comparative example 1 of the present invention.

As can be seen from the above, the drawable, highly conductive material prepared by the embodiment of the present invention can be prepared by a simple ball milling method. The composite conductive material is a high-viscosity semi-solid state, and the viscosity of the composite conductive material is suitable for printing an electronic circuit on the surface of a rigid or flexible substrate by adopting a screen printing mode. The method is simple to operate, can be used for batch preparation, and does not need an additional treatment process. The high-conductivity electronic circuit prepared by the method can meet the application requirements of civil fields such as wearable electronics, electronic skin, intelligent sensing, robots and the like.

It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.

The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.