CN-122007401-A - Liquid gallium-based alloy, preparation method and application thereof

CN122007401ACN 122007401 ACN122007401 ACN 122007401ACN-122007401-A

Abstract

The application provides a liquid gallium-based alloy, a preparation method and application thereof. The liquid gallium-based alloy consists of a plurality of liquid drops, wherein the liquid drops comprise a liquid gallium-based alloy core and a modified coating layer arranged on the surface of the liquid gallium-based alloy core, the liquid gallium-based alloy core comprises 75-83 at% of Ga, 13-17 at% of In, 0.1-7 at% of Sn, 0.1-3 at% of Zn and/or Cd and 0.1-2 at% of Pb and/or Bi according to the atomic percentage, the modified coating layer is made of one or more materials selected from polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, chitosan and cetyltrimethylammonium bromide, the average particle size of the liquid drops is 1-5 mu m, and the electric conductivity is more than or equal to 3.6X10 6 S/m. The liquid drop in the liquid gallium-based alloy provided by the application has high uniformity of size and good dispersibility, is not easy to agglomerate when being used for preparing flexible conductive materials or flexible electronic devices, and can improve the electrical property of the flexible conductive materials or flexible electronic devices.

Inventors

LI YUQING
WANG YIFANG
FU LIN
WANG TONGBO
Ai qin
LOU HUAFEN

Assignees

中铝科学技术研究院有限公司
中铝郑州有色金属研究院有限公司

Dates

Publication Date: 20260512
Application Date: 20260123

Claims (10)

1. The liquid gallium-based alloy is characterized by comprising a plurality of liquid drops, wherein each liquid drop comprises a liquid gallium-based alloy core and a modified coating layer arranged on the surface of the liquid gallium-based alloy core, the liquid gallium-based alloy core comprises 75-83 at% of Ga, 13-17 at% of In, 0.1-7 at% of Sn, 0.1-3 at% of Zn and/or Cd and 0.1-2 at% of Pb and/or Bi according to the atomic percentage, the modified coating layer is made of one or more materials selected from polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, chitosan and cetyltrimethylammonium bromide, the average particle size of the liquid drops is 1-5 mu m, and the electric conductivity is more than or equal to 3.6X10 6 S/m.
2. The liquid gallium-based alloy according to claim 1, wherein the melting point of the liquid gallium-based alloy is less than or equal to 15 ℃, preferably-5-15 ℃; Preferably, the weight average molecular weight of the polyvinylpyrrolidone is 10000-58000, the weight average molecular weight of the polyvinyl alcohol is 10000-80000, the weight average molecular weight of the polyethylene glycol is 2000-20000, and the weight average molecular weight of the chitosan is 50000-300000; preferably, the weight percentage of the modified coating layer is 5-20wt% based on the total weight of the liquid gallium-based alloy; Preferably, the liquid gallium-based alloy core comprises 77-80at% of Ga, 14-16at% of In, 5-7at% of Sn, 2-3at% of Zn and 0.5-1.5at% of Pb, or comprises 77-80at% of Ga, 14-16at% of In, 5-7at% of Sn, 2-3at% of Cd and 0.5-1.5at% of Bi, or comprises 77-80at% of Ga, 14-16at% of In, 5-7at% of Sn, 1-2at% of Zn, 1-2at% of Cd, 0.5-1at% of Pb and 0.5-1at% of Bi; More preferably, the liquid gallium-based alloy core includes the Ga, the In, the Sn, the Zn, the Cd, the Pb, and the Bi, and the atomic number ratio of the Zn to the Cd is 1 (1-3), and the atomic number ratio of the Pb to the Bi is 1 (1-2).
3. A method of preparing the liquid gallium-based alloy according to claim 1 or 2, comprising: step S1, mixing a gallium simple substance, an indium simple substance, a tin simple substance, a zinc simple substance and/or a cadmium simple substance and a lead simple substance and/or a bismuth simple substance to obtain a mixed metal raw material, wherein the molar ratio of the gallium simple substance, the indium simple substance, the tin simple substance, the zinc simple substance and/or the cadmium simple substance to the lead simple substance and/or the bismuth simple substance is (75-83): (13-17): (0.1-7): (0.1-3): (0.1-2); S2, carrying out melting treatment on the mixed metal raw material in an inert atmosphere to obtain a molten material; step S3, cooling the molten material to obtain a liquid material; S4, mixing the liquid material, the solvent and a modified coating agent, and performing ultrasonic treatment to obtain a suspension, wherein the modified coating agent is one or more selected from polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, chitosan and cetyltrimethylammonium bromide; and S5, sequentially carrying out standing sedimentation and centrifugal treatment on the suspension, and drying to obtain the liquid gallium-based alloy.
4. A method of preparing a liquid gallium-based alloy according to claim 3, wherein in step S2, the inert atmosphere is selected from argon and/or nitrogen.
5. The method for producing a liquid gallium-based alloy according to claim 3, wherein in the step S2, the temperature of the melting treatment is 300 to 500 ℃.
6. The method for preparing a liquid gallium-based alloy according to claim 3, wherein the step S3 comprises cooling the molten material to 20-30 ℃ to obtain the liquid material; Preferably, the cooling rate is 1-3 ℃ per minute.
7. The method for producing a liquid gallium-based alloy according to any one of claims 3 to 6, wherein in step S4, the modified cladding agent is 0.1 to 1wt% based on the weight of the suspension, and/or, The weight ratio of the liquid material to the solvent is 1 (20-40), and/or, The solvent is selected from one or more of water, ethanol, propylene glycol, glycerol, formic acid and acetic acid.
8. The method of preparing a liquid gallium-based alloy according to claim 3, wherein in the step S4, the power of the ultrasonic treatment is 400-1000W for 5-30 min, and/or, The ultrasonic treatment is ultrasonic pulse treatment, and the opening time of ultrasonic pulse in each period is 8s, the closing time is 2s, or the opening time is 10s, the closing time is 5s, or the opening time is 20s, and the closing time is 10s.
9. The method for producing a liquid gallium-based alloy according to claim 3, wherein in the step S5, the time for the standing and settling is 1 to 4 hours, and/or, The rotational speed of the centrifugal treatment is 100-1000 rpm, the time is 5-60 min, and/or, The temperature of the drying treatment is 50-80 ℃ and the time is 2-6h.
10. Use of a liquid gallium-based alloy according to claim 1 or 2 for the preparation of a flexible conductive material or flexible electronic device.

Description

Liquid gallium-based alloy, preparation method and application thereof Technical Field The invention relates to the technical field of alloy preparation, in particular to a liquid gallium-based alloy, a preparation method and application thereof. Background In recent years, rapid iteration of electronic science and technology provides strong thrust for rapid development of the wearable electronic field, and the demand of flexible electronic devices with strong elasticity and stretchability and high conductivity is also growing. In the flexible electronic device, the conductive material is used as a core component, the performance quality of the conductive material directly determines the overall performance of the device, and the conductive material can also have key influence on the expansion of the application scene of the device. At present, the traditional conductive materials such as metal, graphene and the like are difficult to meet the requirements of excellent conductivity, good flexibility and reliable mechanical stability. In contrast, liquid metal is used as an emerging material, and is the best choice of conductive material, which is a core component in flexible electronic devices, due to the characteristics of low melting point, strong fluidity, high conductivity, low toxicity, environmental friendliness and the like. However, the liquid metal still faces some challenges in practical application, such as high surface tension, difficulty in wetting most surfaces, easy agglomeration and reduced conductivity after oxidation, which limit the wide popularization of the liquid metal in flexible electronic devices. Therefore, development of a preparation method of micron-sized liquid metal droplets for conductive stretching materials, which can effectively solve the problems, has important significance for promoting development of flexible electronic technology. The prior document (publication No. CN119287203 a) discloses a method for preparing a semi-solid metal elastomer. The invention obtains an aqueous solution of liquid metal liquid drop suspension particles by adding liquid metal into water for ultrasonic mixing, then adds solid metal particles into the aqueous solution, and obtains a mixed suspension of the solid metal particles and the liquid metal liquid drops by ultrasonic mixing. Finally, adding an acidic solution semi-solid metal particles are obtained. The particles can be subsequently used for manufacturing flexible conductive composite materials with high stretchability and high conductivity. However, the liquid metal droplets produced by this method still have poor size uniformity and dispersion stability. On the basis, a preparation method of the liquid gallium-based alloy capable of improving the fluidity and the conductivity of the liquid gallium-based alloy and improving the size uniformity and the dispersion stability of the liquid gallium-based alloy is researched and developed, and the preparation method has important significance for improving the performance of flexible electronic devices. Disclosure of Invention The invention mainly aims to provide a liquid gallium-based alloy, a preparation method and application thereof, and aims to solve the problems of poor fluidity and conductivity, poor size uniformity and poor dispersion stability of the liquid gallium-based alloy in the prior art. In order to achieve the above purpose, the invention provides a liquid gallium-based alloy, which comprises a plurality of liquid drops, wherein the liquid drops comprise a liquid gallium-based alloy core and a modified coating layer arranged on the surface of the liquid gallium-based alloy core, the liquid gallium-based alloy core comprises 75-83 at% of Ga, 13-17 at% of In, 0.1-7 at% of Sn, 0.1-3 at% of Zn and/or Cd and 0.1-2 at% of Pb and/or Bi according to the atomic percentage, the modified coating layer is made of one or more materials selected from polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, chitosan and cetyltrimethylammonium bromide, the average particle size of the liquid drops is 1-5 mu m, and the electric conductivity is more than or equal to 3.6X10 6 S/m. Further, the melting point of the liquid gallium-based alloy is less than or equal to 15 ℃, and is preferably-5-15 ℃. Further, the weight average molecular weight of polyvinylpyrrolidone is 10000-58000, the weight average molecular weight of polyvinyl alcohol is 10000-80000, the weight average molecular weight of polyethylene glycol is 2000-20000, and the weight average molecular weight of chitosan is 50000-300000. Further, the weight percentage of the modified coating layer is 5-20wt% based on the total weight of the liquid gallium-based alloy. Further, the liquid gallium-based alloy core comprises, by atomic percentage, 77-80 at% Ga, 14-16 at% In, 5-7 at% Sn, 2-3 at% Zn, and 0.5-1.5 at% Pb, or the liquid gallium-based alloy core comprises 77-80 at% Ga, 14-16 at% In, 5-7 at% Sn, 1-2 at% Cd, and 0.5-1.5 at% Bi,