A two-phase metal gel and a method for preparing the same

Abstract

The application discloses a kind of two-phase metal gels and preparation method thereof, belong to gel and polymer composite material technical field.The steps include: rigid metal particles and flexible liquid metal are mixed in acidic solution or alkaline solution, separate after continuous stirring, obtain two-phase metal;Polyvinyl alcohol is dissolved in good solvent, obtain polyvinyl alcohol solution;Two-phase metal and polyvinyl alcohol solution are mixed and dispersed, obtain two-phase metal-polyvinyl alcohol mixed solution;Two-phase metal-polyvinyl alcohol mixed solution is dried, obtain two-phase metal gel.Compared with prior art, two-phase metal gel of the application has high electron conductivity, high toughness and flexibility.

Description

Technical Field

[0001] This invention relates to the field of gel and polymer composite materials technology, and more specifically, to a two-phase metal gel, its preparation method, and its application in flexible electronic products. Background Technology

[0002] The development of flexible electronics requires flexible materials to simultaneously achieve high conductivity and high toughness. Among these, achieving 10... 6 Metallic conductivity above S / m can reduce the internal resistance of devices, thereby improving signal transmission quality and minimizing energy consumption. Simultaneously, high toughness ensures the stability of the device structure, enabling it to withstand unavoidable damage during use, such as stretching, tearing, or puncture, and reducing resource waste and environmental pollution, thus contributing to the sustainable development of electronic products.

[0003] However, currently developed materials cannot achieve a combination of high conductivity, high toughness, and flexibility. Among these, metallic conductors have a conductivity exceeding (10⁻⁶). 6 Its conductivity is (S / m), but its inherent rigidity makes it unsuitable for flexible electronic products. Additionally, materials based on conductive polymers, such as polyaniline and polypyrrole, have low conductivity (10 S / m). -1 -10 4 (S / m), and typically exhibits values ​​below 5 MJ / m 3 The toughness of the composite material is insufficient to meet the requirements. To overcome these limitations, composite materials developed by incorporating conductive fillers into the polymer matrix are expected to possess both high conductivity and high toughness. However, while adding a small amount of conductive filler can improve toughness, the conductivity of such composite materials is not ideal (10⁻⁶) due to the lack of continuous conductive pathways. 1 -10 5 Increasing the content of conductive filler can significantly improve electrical conductivity, but a high content of rigid filler can lead to the formation of more defects within the material, making it brittle overall. Conversely, in our laboratory's related research (Adv. Mater. 2024, 2409137. Doi:10.1002 / adma.202409137), we found that adding more flexible filler, such as liquid metal, can improve the electrical properties of the material, but at the same time, it will reduce the mechanical strength of the material, resulting in lower toughness (<3 MJ / m). 3 Therefore, there are still significant challenges in developing flexible materials that possess both metallic conductivity and high toughness. Summary of the Invention

[0004] 1. Technical problems to be solved

[0005] To address the problem that existing flexible materials cannot simultaneously possess both metallic-grade electronic conductivity and high toughness, this invention aims to develop a novel material based on relevant research in our laboratory. This material will possess both metallic-grade electronic conductivity and high toughness, thereby meeting the requirements of flexible electronic products for conductivity and toughness.

[0006] 2. Technical Solution

[0007] To achieve the above objectives, this invention provides a two-phase metal gel material in which a continuous phase is formed within the material and fixed by a three-dimensional continuous polymer network, achieving metallic-grade electrical conductivity. Furthermore, due to the excellent interfaces between the two-phase metals and between the two-phase metals and the polymers, effective stress transfer is achieved within the gel, resulting in three stress dissipation modes and high toughness. Specifically, the objectives of this invention are achieved through the following technical solutions:

[0008] [Preparation methods of two-phase metal gels and the prepared two-phase metal gels]

[0009] The first aspect of this invention provides a method for preparing a two-phase metal gel, comprising the following steps:

[0010] Preparation of two-phase metals: Rigid metal particles and flexible liquid metals are mixed in an acidic or alkaline solution, stirred continuously, and then separated to obtain two-phase metals;

[0011] Preparation of polyvinyl alcohol solution: Polyvinyl alcohol particles are dissolved in a good solvent to obtain a polyvinyl alcohol solution;

[0012] Preparation of a two-phase metal-polyvinyl alcohol mixed solution: The two-phase metal is mixed and dispersed with the polyvinyl alcohol solution to obtain a two-phase metal-polyvinyl alcohol mixed solution;

[0013] Drying: The two-phase metal-polyvinyl alcohol mixed solution is dried to obtain a two-phase metal gel.

[0014] This invention utilizes a two-phase metal formed by rigid metal particles and flexible liquid metal, dispersed within a continuous polyvinyl alcohol (PVA) polymer network. The rigid metal particles provide toughness to the two-phase metal gel. The metal-wetting interaction between the rigid metal particles and the flexible liquid metal, as well as the hydrogen bonding between the flexible liquid metal and the PVA network, establish a favorable interface, promoting stress transfer between the components. Therefore, when the material deforms, the applied force causes deformation of the polymer network, resulting in energy dissipation. Simultaneously, the flexible liquid metal deforms synchronously with the polymer network, contributing to additional energy dissipation, while the rigid metal particles, acting as stress concentration points, also absorb some of the applied energy. Furthermore, the two-phase metal formed by rigid metal particles and flexible liquid metal overcomes the problem of low electronic conductivity in metal gels formed by liquid metal and PVA.

[0015] As a preferred embodiment of the step in preparing the two-phase metal in this invention, the rigid metal particles are selected from one or more of iron, nickel, copper, silver, gold, or neodymium iron boron alloys; the selection of metal particles needs to meet the requirements of both rigidity and high electrical conductivity at the same time, therefore non-conductive metals such as aluminum cannot be selected as rigid metal particles to form a two-phase metal with the flexible liquid metal;

[0016] More preferably, the rigid metal particles are copper, and copper powder and liquid metal can form an intermetallic compound CuGa2. The resulting copper-two-phase metal gel has significantly higher toughness than other rigid metal particle two-phase metal gels.

[0017] More preferably, the particle size of the rigid metal is 50 nm to 10 μm. For example, data from the preparation examples show that two-phase metal gels prepared from copper powder in the 50 nm to 10 μm particle size range all exhibit good electronic conductivity and toughness;

[0018] Preferably, the flexible liquid metal is selected from one or two of gallium-indium alloy and gallium-indium-tin alloy. Although mercury, cesium, francium and other metals are also liquid metals, their applications are greatly limited due to their toxicity, radioactivity or danger. Gallium, indium, tin metals and their alloys are the most widely researched and applied liquid metal materials due to their safety, non-toxicity and excellent performance.

[0019] More preferably, the mass fraction of Ga in the gallium-indium alloy is 75.50%. wt And In 24.50% wt The mass fraction of Ga in the gallium-indium-tin alloy is 68.50%. wt ,、In 21.50% wt and Sn 10.00% wt ;

[0020] Preferably, the weight ratio of the rigid metal particles to the flexible liquid metal is between 1:6 and 1:20, and most preferably 1:12; this ensures that the rigid metal particles are completely immersed in the flexible liquid metal and that the rigid metal particles effectively improve the electrical conductivity of the two-phase metal in the polymer network.

[0021] Preferably, the prepared two-phase metal is one or more of the following: iron-gallium-indium alloy two-phase metal, nickel-gallium-indium alloy two-phase metal, copper-gallium-indium alloy two-phase metal, silver-gallium-indium alloy two-phase metal, gold-gallium-indium alloy two-phase metal, neodymium iron boron alloy-gallium-indium alloy two-phase metal, iron-gallium-indium-tin alloy two-phase metal, nickel-gallium-indium-tin alloy two-phase metal, copper-gallium-indium-tin alloy two-phase metal, silver-gallium-indium-tin alloy two-phase metal, gold-gallium-indium-tin alloy two-phase metal, or neodymium iron boron alloy-gallium-indium-tin alloy two-phase metal;

[0022] Data from the examples show that the electronic conductivity of the two-phase metal gel materials prepared using the above-described two-phase metal is greater than or equal to 2.00 × 10⁻⁶. 6 S / m and toughness are both greater than or equal to 7 MJ·m 3 The Young's modulus values ​​are all less than or equal to 7 MPa, achieving a balance between high electronic conductivity, high toughness, and flexibility.

[0023] Preferably, the concentration of the acidic or alkaline solution is 1-4 M; more preferably, the volume ratio of the two-phase metal to the acidic or alkaline solution is less than 1:5, and more preferably less than 1:10.

[0024] Acidic or alkaline solutions primarily provide conditions for the uniform mixing of rigid metal particles and flexible liquid metal.

[0025] Preferably, rigid metal particles and flexible liquid metal are mixed in an acidic or alkaline solution and stirred continuously for 0.5 to 1 hour at a stirring speed of 8000 rpm to 15000 rpm.

[0026] Rigid metal particles can be completely wetted and uniformly dispersed in flexible liquid metal, making the two-phase metal homogeneous and ensuring the uniformity of electrical conductivity and stable electromechanical coupling performance of the two-phase metal; at the same time, it improves the strength and compatibility of conductive fillers, so as to form a stable interface with polyvinyl alcohol polymer network.

[0027] As a preferred step in preparing the polyvinyl alcohol solution according to the present invention, 8 wt%-12 wt% of polyvinyl alcohol particles are dissolved in a good solvent and continuously magnetically stirred at a temperature above 95°C for 1 hour until dissolved.

[0028] More preferably, 10 wt% of polyvinyl alcohol particles are dissolved in a good solvent and continuously magnetically stirred at 95°C for 1 hour until dissolved;

[0029] More preferably, the good solvent is one or both of deionized water and dimethyl sulfoxide (DMSO).

[0030] As a preferred step in preparing the two-phase metal-polyvinyl alcohol mixed solution of the present invention, the two-phase metal and the polyvinyl alcohol solution are mixed and dispersed in a weight ratio of 1:1 to 7:3, and most preferably 13:7.

[0031] The above ratio ensures that the two-phase metals are interconnected throughout the material, forming a continuous phase, which provides a good electronic pathway for the two-phase metal gel; it also ensures that the polyvinyl alcohol polymer network presents a continuous three-dimensional porous structure, which provides good mechanical support for the two-phase metal gel.

[0032] More preferably, the mixing and dispersion method is to use a hand-held homogenizer to stir and shear at a speed of 8000 rpm to 15000 rpm for 5 min to 15 min.

[0033] After undergoing high-speed stirring and shearing in a homogenizer, the two-phase metals form micron-sized droplets dispersed in the solution, with the polymer network partially encapsulating the metal surface and the remainder dispersed in a good solvent.

[0034] As a preferred step in the drying process of this invention, the obtained two-phase metal-polyvinyl alcohol mixed solution is added to a polytetrafluoroethylene petri dish and placed in an environment of 25°C to 80°C to remove the good solvent.

[0035] Further optimization involves adding the obtained two-phase metal-polyvinyl alcohol mixed solution into a polytetrafluoroethylene petri dish and placing it in an environment at 60°C to remove the good solvent.

[0036] As drying proceeds, polyvinyl alcohol molecules physically crosslink to form a three-dimensional network, and the two-phase metals gradually approach each other. Finally, after demolding, the two-phase metals form a continuous phase, and the three-dimensional continuous polyvinyl alcohol polymer network within the continuous two-phase metal phase maintains the stability of the material.

[0037] The second aspect of the present invention provides a two-phase metal gel prepared by a method for preparing a two-phase metal gel according to any embodiment of the first aspect of the present invention.

[0038] As a preferred embodiment of the two-phase metal gel of the second aspect of the present invention, the electronic conductivity of the two-phase metal gel is greater than or equal to 2.00 × 10⁻⁶. 6 S / m, toughness greater than or equal to 7 MJ·m 3 The value of Young's modulus is less than or equal to 7 MPa.

[0039] [Binary Metal Gel]

[0040] A third aspect of the present invention provides a two-phase metal gel comprising a two-phase metal and polyvinyl alcohol, wherein the two-phase metal is dispersed in polyvinyl alcohol;

[0041] The two-phase metal comprises rigid metal particles and flexible liquid metal;

[0042] In the two-phase metal, the rigid metal particles have a size of 50 nm to 10 μm;

[0043] In the two-phase metal, the mass ratio of rigid metal particles to flexible liquid metal is 1:(6-20);

[0044] The mass ratio of the two-phase metal to polyvinyl alcohol is (30-70):3.

[0045] This invention utilizes a two-phase metal formed by rigid metal particles and flexible liquid metal, dispersed within a continuous polyvinyl alcohol (PVA) polymer network. The rigid metal particles provide toughness to the two-phase metal gel. The metal-wetting interaction between the rigid metal particles and the flexible liquid metal, as well as the hydrogen bonding between the flexible liquid metal and the PVA network, establish a favorable interface, promoting stress transfer between the components. Therefore, when the material deforms, the applied force causes deformation of the polymer network, resulting in energy dissipation. Simultaneously, the flexible liquid metal deforms synchronously with the polymer network, contributing to additional energy dissipation, while the rigid metal particles, acting as stress concentration points, also absorb some of the applied energy. Furthermore, the two-phase metal formed by rigid metal particles and flexible liquid metal overcomes the problem of low electronic conductivity in metal gels formed by liquid metal and PVA.

[0046] As a preferred embodiment of the two-phase metal gel of the third aspect of the present invention, the rigid metal particles are selected from one or more of iron, nickel, copper, silver, gold or neodymium iron boron alloys.

[0047] The flexible liquid metal is selected from one or both of gallium indium alloy and gallium indium tin alloy.

[0048] As a preferred embodiment of the two-phase metal gel of the third aspect of the present invention, the rigid metal particles are copper.

[0049] As a preferred embodiment of the binary metal gel in the third aspect of the present invention, the binary metal is selected from one or more of the following: iron-gallium indium alloy binary metal, nickel-gallium indium alloy binary metal, copper-gallium indium alloy binary metal, silver-gallium indium alloy binary metal, gold-gallium indium alloy binary metal, neodymium iron boron alloy-gallium indium alloy binary metal, iron-gallium indium tin alloy binary metal, nickel-gallium indium tin alloy binary metal, copper-gallium indium tin alloy binary metal, silver-gallium indium tin alloy binary metal, gold-gallium indium tin alloy binary metal, and neodymium iron boron alloy-gallium indium tin alloy binary metal.

[0050] As a preferred embodiment of the two-phase metal gel in the third aspect of the present invention, the flexible liquid metal is a gallium-indium alloy, wherein the mass ratio of gallium to indium in the gallium-indium alloy is 75.50:24.5; or

[0051] The flexible liquid metal is a gallium indium tin alloy, wherein the mass ratio of gallium, indium, and tin in the gallium indium tin alloy is 68.50:21.50:10.00.

[0052] As a preferred embodiment of the biphase metal gel in the third aspect of the present invention, the electronic conductivity of the biphase metal gel is greater than or equal to 2.00 × 10⁻⁶. 6 S / m, toughness greater than or equal to 7 MJ·m 3 The value of Young's modulus is less than or equal to 7 MPa.

[0053] The two-phase metal gel of the third aspect of the present invention can be prepared by using the preparation method provided in the first aspect of the present invention.

[0054] Flexible electronic products

[0055] A fourth aspect of the present invention provides a flexible electronic product comprising a two-phase metal gel as described in any embodiment of the second aspect of the present invention or any embodiment of the third aspect of the present invention.

[0056] The present invention relates to a novel highly conductive and highly tough flexible electronic product comprising a two-phase metal gel composed of a two-phase metal and polyvinyl alcohol; wherein the two-phase metal forms a continuous body as the fluid phase of the gel; a three-dimensional continuous polyvinyl alcohol polymer network fixes the two-phase metal fluid through interactions; and there are good interfaces between the two-phase metals and between the metal and the polymer network, which gives the two-phase metal gel and the flexible electronic product containing the two-phase metal gel superior toughness.

[0057] 3. Beneficial effects

[0058] Compared with the prior art, the advantages of this invention are:

[0059] (1) The two-phase metal gel prepared by the method of the present invention has developed a new material system and realized for the first time the use of two-phase metal as a continuous conductive phase in gel material; through the droplet with a three-layer core-shell structure formed by two-phase metal and polymer, a material structure completely different from the existing liquid metal composite material was obtained;

[0060] In addition, this invention achieves metal-level electronic conductivity by fixing a two-phase metal continuum in a three-dimensional polymer network; and, due to the good compatibility interface between the rigid metal particles, the flexible liquid metal and the polymer network, stress transmission between components is enhanced, resulting in three energy dissipation modes within the material, thereby enabling the composite material to obtain excellent toughness, and ultimately obtaining a two-phase metal gel that combines high electronic conductivity, toughness and flexibility.

[0061] (2) The different rigid metal particles used in this invention can form a two-phase metal with liquid metal, which improves the strength and compatibility of the conductive filler, can form a stable interface with the polymer network, and can maintain the stability of structure and performance even after the material has undergone repeated physical deformation or extreme damage.

[0062] (3) The series of two-phase metal gels prepared by this invention all exhibit high electronic conductivity and high toughness, such as Figure 15 As shown, compared with other high-conductivity composite materials in the prior art, the two-phase metal gel of the present invention stands out in achieving both high conductivity and high toughness; specifically, compared with existing high-conductivity composite materials, the toughness of the two-phase metal gel is improved by at least 6.4 times. Attached Figure Description

[0063] Figure 1 A schematic diagram of a computed tomography image of the two-phase metal gel (liquid metal: copper: polyvinyl alcohol = 12:1:7) prepared in Example 1 of the present invention;

[0064] Figure 2 This is a schematic diagram of the polyvinyl alcohol polymer network extracted from a computed tomography image of the two-phase metal gel (liquid metal: copper: polyvinyl alcohol = 12:1:7) prepared in Example 1 of the present invention.

[0065] Figure 3 This is a schematic diagram of the three-layer core-shell structured droplet formed by copper-gallium-indium alloy two-phase metal and polyvinyl alcohol in Example 1 of the present invention.

[0066] Figure 4 This is a schematic diagram of the preparation process of the two-phase metal gel in the preparation example of the present invention;

[0067] Figure 5 This is a statistical schematic diagram of the electronic conductivity of the two-phase metal gel obtained from the copper-gallium-indium alloy and polyvinyl alcohol in Example 1 of the present invention.

[0068] Figure 6 This is a schematic diagram showing the stress-strain curves, toughness, and flexibility of the two-phase metal gel obtained from the copper-gallium-indium alloy and polyvinyl alcohol in Example 1 of this invention.

[0069] Figure 7 This is a fracture energy curve and a schematic diagram of the fracture energy performance of the two-phase metal gel obtained from the copper-gallium-indium alloy and polyvinyl alcohol in Example 1 of the present invention.

[0070] Figure 8 Optical photographs taken before and after stirring when copper powder and liquid metal (gallium indium alloy: copper = 12:1) were added to a 1M hydrochloric acid solution in Example 1 of this invention.

[0071] Figure 9 :

[0072] (a) is the X-ray diffraction (XRD) pattern of copper powder-liquid metal (gallium indium alloy: copper = 12:1);

[0073] (b) is the X-ray diffraction (XRD) pattern of iron powder-liquid metal (gallium indium alloy: iron = 6:1);

[0074] Figure 10 This is a schematic diagram showing the stress-strain curves, toughness, flexibility, and conductivity of the iron-gallium-indium alloy two-phase metal gel prepared in Example 2 of this invention.

[0075] Figure 11This is a schematic diagram showing the stress-strain curves, toughness, flexibility, and conductivity of the iron-gallium-indium-tin alloy two-phase metal gel prepared in Example 3 of this invention.

[0076] Figure 12 This is a schematic diagram showing the stress-strain curves, toughness, flexibility, and electrical conductivity of the nickel-gallium-indium alloy two-phase metal gel prepared in Example 4 of this invention.

[0077] Figure 13 This is a schematic diagram showing the stress-strain curves, toughness, flexibility, and conductivity of the iron-gallium-indium alloy two-phase metal gel prepared in Example 5 of this invention.

[0078] Figure 14 This is a schematic diagram showing the stress-strain curves, toughness, flexibility, and electrical conductivity of the nickel-gallium-indium alloy two-phase metal gel prepared in Example 6 of this invention.

[0079] Figure 15 This is a schematic diagram comparing the conductivity and toughness of the two-phase metal gel obtained from copper-gallium-indium alloy and polyvinyl alcohol in Example 1 of the present invention with the performance of other flexible conductive materials.

[0080] Figure 16 This is a schematic diagram illustrating the performance of two-phase metal gels prepared with different copper powder particle sizes in Example 8 of this invention. Detailed Implementation

[0081] The present invention will now be described in detail with reference to the accompanying drawings and specific preparation examples.

[0082] Preparation Example

[0083] Preparation materials

[0084] Copper powder (50-100nm particle size, 1μm particle size) was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.; iron powder (1μm particle size) was purchased from Alfaisa (China) Chemical Co., Ltd.; nickel powder (1μm particle size) was purchased from Anhui Zesheng Technology Co., Ltd.; neodymium iron boron alloy (1μm particle size) was purchased from Qinghe County Benyu Metal Materials Co., Ltd.; silver powder (1μm particle size), gold powder (1μm particle size), and copper powder (5-10μm particle size) were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; gallium indium alloy (Ga 75.50%)... wt ;In 24.50% wt Gallium indium tin alloy (Ga 68.50%) wt ,;In 21.50% wt Sn 10.00% wt Purchased from Dongguan Dingyi Metal Co., Ltd., and polyvinyl alcohol granules (1750±50) purchased from Shanghai Yuanye Biotechnology Co., Ltd.

[0085] The copper powder used in Preparation Examples 1-7 was copper powder with a particle size of 1 μm; the copper powder used in Preparation Example 8 was copper powder with a particle size of 50-100 nm, 1 μm, and 5-10 μm.

[0086] Preparation Example 1

[0087] like Figure 4 As shown, this embodiment discloses a method for preparing a two-phase metal gel, including the following steps:

[0088] Preparation of two-phase metals:

[0089] Preparation of copper-gallium-indium alloy two-phase metals:

[0090] Specifically, copper powder particles and gallium-indium alloy (the weight ratio of copper powder particles to gallium-indium alloy is 1:12) are added to a 1M hydrochloric acid solution. The volume ratio of hydrochloric acid to metal is approximately 5:1. The mixture is continuously magnetically stirred at room temperature for 1 hour until the copper powder particles are completely immersed in the gallium-indium alloy. After washing off the hydrochloric acid, a copper-gallium-indium alloy two-phase metal is obtained.

[0091] Preparation of silver-gallium-indium alloy two-phase metal:

[0092] Specifically, silver powder particles and gallium-indium alloy (the weight ratio of silver powder particles to gallium-indium alloy is 1:12) are added to a 1M hydrochloric acid solution. The volume ratio of hydrochloric acid to metal is approximately 5:1. The mixture is continuously magnetically stirred at room temperature for 1 hour until the silver powder particles are completely immersed in the gallium-indium alloy. After washing off the hydrochloric acid, a silver-gallium-indium alloy two-phase metal is obtained.

[0093] Preparation of gold-gallium-indium alloy two-phase metals:

[0094] Specifically, gold powder particles and gallium-indium alloy (the weight ratio of gold powder particles to gallium-indium alloy is 1:12) are added to a 1M hydrochloric acid solution. The volume ratio of hydrochloric acid to metal is approximately 5:1. The mixture is continuously magnetically stirred at room temperature for 1 hour until the gold powder particles are completely immersed in the gallium-indium alloy. After washing off the hydrochloric acid, a gold-gallium-indium alloy two-phase metal is obtained.

[0095] Preparation of copper-gallium-indium-tin alloy two-phase metal:

[0096] Specifically, copper powder particles and gallium indium tin alloy (the weight ratio of copper powder particles to gallium indium tin alloy is 1:12) are added to a 1M hydrochloric acid solution. The volume ratio of hydrochloric acid to metal is about 5:1. The mixture is continuously magnetically stirred at room temperature for 1 hour until the copper powder particles are completely immersed in the gallium indium tin alloy. After washing off the hydrochloric acid, a copper-gallium indium tin alloy two-phase metal is obtained.

[0097] Preparation of silver-gallium-indium-tin alloy two-phase metal:

[0098] Specifically, silver powder particles and gallium indium tin alloy (the weight ratio of silver powder particles to gallium indium tin alloy is 1:12) are added to a 1M hydrochloric acid solution. The volume ratio of hydrochloric acid to metal is about 5:1. The mixture is continuously magnetically stirred at room temperature for 1 hour until the silver powder particles are completely immersed in the gallium indium tin alloy. After washing off the hydrochloric acid, a silver-gallium indium tin alloy two-phase metal is obtained.

[0099] Preparation of gold-gallium-indium-tin alloy two-phase metal:

[0100] Specifically, gold powder particles and gallium indium tin alloy (the weight ratio of gold powder particles to gallium indium tin alloy is 1:12) are added to a 1M hydrochloric acid solution. The volume ratio of hydrochloric acid to metal is about 5:1. The mixture is continuously magnetically stirred at room temperature for 1 hour until the gold powder particles are completely immersed in the gallium indium tin alloy. After washing off the hydrochloric acid, a gold-gallium indium tin alloy two-phase metal is obtained.

[0101] Preparation of iron-gallium-indium alloy two-phase metals:

[0102] Specifically, iron powder particles and gallium indium alloy (the weight ratio of iron powder particles to gallium indium alloy is 1:6) are added to a 1M hydrochloric acid solution. The volume ratio of hydrochloric acid to metal is approximately 5:1. The mixture is stirred continuously at room temperature for 30 minutes until the iron powder particles are completely immersed in the gallium indium alloy. After washing off the hydrochloric acid, an iron-gallium indium alloy two-phase metal is obtained.

[0103] Preparation of nickel-gallium-indium alloy two-phase metals:

[0104] Specifically, nickel powder particles and gallium indium alloy (the weight ratio of nickel powder particles to gallium indium alloy is 1:6) are added to a 1M hydrochloric acid solution. The volume ratio of hydrochloric acid to metal is approximately 5:1. The mixture is stirred continuously at room temperature for 30 minutes until the nickel powder particles are completely immersed in the gallium indium alloy. After washing off the hydrochloric acid, a nickel-gallium indium alloy two-phase metal is obtained.

[0105] Preparation of NdFeB alloy-GaIn alloy two-phase metals:

[0106] Specifically, neodymium iron boron alloy particles and gallium indium alloy (the weight ratio of neodymium iron boron alloy particles to gallium indium alloy is 1:6) are added to a 1M hydrochloric acid solution. The volume ratio of hydrochloric acid to metal is approximately 5:1. The mixture is stirred continuously at room temperature for 30 minutes until the neodymium iron boron alloy particles are completely immersed in the gallium indium alloy. After washing off the hydrochloric acid, a neodymium iron boron alloy-gallium indium alloy two-phase metal is obtained.

[0107] Preparation of iron-gallium-indium-tin alloy two-phase metals:

[0108] Specifically, iron powder particles and gallium indium tin alloy (weight ratio of iron powder particles to gallium indium tin alloy is 1:6) are added to a 1M hydrochloric acid solution. The volume ratio of hydrochloric acid to metal is approximately 5:1. The mixture is stirred continuously at room temperature for 30 minutes until the iron powder particles are completely immersed in the gallium indium tin alloy. After washing off the hydrochloric acid, an iron-gallium indium tin alloy two-phase metal is obtained.

[0109] Preparation of nickel-gallium-indium-tin alloy two-phase metal:

[0110] Specifically, nickel powder particles and gallium indium tin alloy (the weight ratio of nickel powder particles to gallium indium tin alloy is 1:6) are added to a 1M hydrochloric acid solution. The volume ratio of hydrochloric acid to metal is approximately 5:1. The mixture is stirred continuously at room temperature for 30 minutes until the nickel powder particles are completely immersed in the gallium indium tin alloy. After washing off the hydrochloric acid, a nickel-gallium indium tin alloy two-phase metal is obtained.

[0111] Preparation of NdFeB alloy-GaInTin alloy two-phase metals:

[0112] Specifically, neodymium iron boron alloy particles and gallium indium tin alloy (the weight ratio of neodymium iron boron alloy particles to gallium indium tin alloy is 1:6) are added to a 1M hydrochloric acid solution. The volume ratio of hydrochloric acid to metal is approximately 5:1. The mixture is stirred continuously at room temperature for 30 minutes until the neodymium iron boron alloy particles are embedded inside the gallium indium tin alloy. After washing off the hydrochloric acid, a neodymium iron boron alloy-gallium indium tin alloy two-phase metal is obtained.

[0113] Preparation of polyvinyl alcohol solution:

[0114] Specifically, the steps for preparing a polyvinyl alcohol solution are as follows: dissolve 10 wt% of polyvinyl alcohol particles in deionized water, and continuously stir magnetically at 95°C for 1 hour until dissolved to obtain a polyvinyl alcohol solution.

[0115] Preparation of a two-phase metal-polyvinyl alcohol mixed solution:

[0116] The copper-gallium indium alloy, silver-gallium indium alloy, gold-gallium indium alloy, copper-gallium indium tin alloy, silver-gallium indium tin alloy, and gold-gallium indium tin alloy were respectively mixed with a polyvinyl alcohol solution at a weight ratio of 13:7.

[0117] The above-mentioned iron-gallium indium alloy two-phase metal, nickel-gallium indium alloy two-phase metal, neodymium iron boron alloy-gallium indium alloy two-phase metal, iron-gallium indium tin alloy two-phase metal, nickel-gallium indium tin alloy two-phase metal, and neodymium iron boron alloy-gallium indium tin alloy two-phase metal were respectively mixed with polyvinyl alcohol solution at a weight ratio of 7:7.

[0118] Then, at room temperature, each of the mixed solutions was stirred and sheared at 15,000 rpm for 5 minutes using a handheld homogenizer to obtain uniformly dispersed two-phase metal-polyvinyl alcohol mixed solutions of twelve systems.

[0119] dry:

[0120] The uniformly dispersed two-phase metal-polyvinyl alcohol mixture was heated to remove the good solvent.

[0121] Specifically, the obtained two-phase metal-polyvinyl alcohol mixed solutions of the twelve systems were added to polytetrafluoroethylene petri dishes, and then placed in an environment of 60°C to remove the good solvent, resulting in twelve two-phase metal gels.

[0122] Table 1. Weight ratios of liquid metal to rigid metal and polyvinyl alcohol solutions, Young's modulus, electronic conductivity, and toughness of twelve two-phase metal gels.

[0123]

[0124]

[0125] As shown in Table 1, following the steps described above, two-phase metal gels can be successfully prepared using different two-phase metals (iron-gallium-indium alloy, nickel-gallium-indium alloy, copper-gallium-indium alloy, silver-gallium-indium alloy, gold-gallium-indium alloy, NdFeB-gallium-indium alloy, iron-gallium-indium-tin alloy, nickel-gallium-indium-tin alloy, copper-gallium-indium-tin alloy, silver-gallium-indium-tin alloy, gold-gallium-indium-tin alloy, and NdFeB-gallium-indium-tin alloy) and polyvinyl alcohol. Furthermore, the prepared two-phase metal gels all exhibit excellent electronic conductivity, high toughness, and appropriate flexibility.

[0126] Specifically, the electronic conductivity of the prepared two-phase metal gel materials is greater than 2.00 × 10⁻⁶. 6 Both S / m and toughness are higher than 7 MJ·m. 3 The Young's modulus values ​​are all below 7 MPa, achieving a balance between high electronic conductivity, high toughness, and flexibility.

[0127] like Figure 1 The image shown is a computed tomography (CT) image of the two-phase metal gel (liquid metal: copper: polyvinyl alcohol = 12:1:7) prepared in Example 1 of this invention.

[0128] Among them, the two-phase metal, as the fluid phase in the two-phase metal gel, is an interconnected continuum, in which liquid metal accounts for 75.54% of the volume fraction and rigid metal particles account for 2.09% of the volume fraction; as a three-dimensional continuous polymer network, polyvinyl alcohol accounts for 22.37% of the volume fraction.

[0129] like Figure 2 As shown, Figure 1 A schematic diagram of the polyvinyl alcohol polymer network extracted from a computed tomography image.

[0130] like Figure 3 The diagram shown is a schematic representation of the three-layer core-shell structure of the droplet formed by the copper-gallium indium alloy two-phase metal and polyvinyl alcohol in Example 1.

[0131] like Figure 5 The figure shows a statistical diagram of the electronic conductivity of copper-gallium-indium alloy two-phase metal gel. The conductivity of the copper-gallium-indium alloy two-phase metal gel exhibits good repeatability and stable electromechanical coupling properties, with a maximum conductivity reaching 2.52 × 10⁻⁶. 6 S / m.

[0132] like Figure 6 The figure shows the stress-strain curves of the copper-gallium-indium alloy two-phase metal gel and a schematic diagram of its corresponding toughness and flexibility. The copper-gallium-indium alloy two-phase metal gel exhibits an average toughness of 14.40 MJ / m. 3 The average Young's modulus is 6.80 MPa.

[0133] like Figure 7 The figure shows the fracture energy curve and corresponding performance diagram of the copper-gallium-indium alloy two-phase metal gel. The average fracture energy of the copper-gallium-indium alloy two-phase metal gel is 20.41 kJ / m. 2 .

[0134] like Figure 8 The image shows optical photographs before and after stirring a 1M hydrochloric acid solution containing copper powder and liquid metal (gallium-indium alloy: copper = 12:1). The optical images show that the copper powder is completely embedded within the liquid metal.

[0135] like Figure 9 (a) shows the X-ray diffraction (XRD) pattern of copper powder-liquid metal (gallium indium alloy: copper = 12:1);

[0136] like Figure 9 (b) shows the X-ray diffraction (XRD) pattern of iron powder-liquid metal (gallium indium alloy: iron = 6:1);

[0137] Depend on Figure 9 As can be seen, copper powder and liquid metal formed an intermetallic compound CuGa2, while iron powder and liquid metal did not form an intermetallic compound. This is the reason why the toughness of copper two-phase metal gel is significantly higher than that of other rigid metal particle two-phase metal gels.

[0138] like Figure 15 As shown, the conductivity and toughness of copper-gallium indium alloy two-phase metal gel far exceed the performance of other flexible conductive materials.

[0139] Preparation Example 2

[0140] Preparation of iron-gallium-indium alloy two-phase metals:

[0141] Specifically, iron powder particles and gallium-indium alloy (the weight ratio of iron powder particles to gallium-indium alloy is 1:7) are added to a 1M hydrochloric acid solution, and the volume ratio of hydrochloric acid to metal is 5:1. The mixture is stirred continuously at room temperature for 30 minutes until the iron powder particles are completely immersed in the gallium-indium alloy. After washing off the hydrochloric acid, an iron-gallium-indium alloy two-phase metal is obtained.

[0142] Preparation of polyvinyl alcohol solution:

[0143] Specifically, the steps for preparing a polyvinyl alcohol solution are as follows: dissolve 10 wt% of polyvinyl alcohol particles in deionized water, and continuously stir magnetically at 95°C for 1 hour until dissolved to obtain a polyvinyl alcohol solution.

[0144] Preparation of a two-phase metal-polyvinyl alcohol mixed solution:

[0145] The above-mentioned two-phase metal was mixed with a polyvinyl alcohol solution at a weight ratio of 2:1, and then stirred and sheared at 15,000 rpm for 5 minutes at room temperature using a hand-held homogenizer to obtain an iron-gallium-indium alloy two-phase metal-polyvinyl alcohol mixed solution.

[0146] dry:

[0147] The uniformly dispersed mixed solution is heated to remove the good solvent.

[0148] Specifically, the obtained iron-gallium indium alloy two-phase metal-polyvinyl alcohol mixed solution was added to a polytetrafluoroethylene petri dish, and then placed in an environment of 60°C to remove the good solvent, thereby obtaining an iron-gallium indium alloy two-phase metal gel.

[0149] like Figure 10 As shown, the electronic conductivity of the iron-gallium-indium alloy two-phase metal gel is 2.10 × 10⁻⁶. 6 S / m, toughness is 8.48 MJ / m 3 The Young's modulus is 5.58 MPa.

[0150] Preparation Example 3

[0151] Preparation of iron-gallium-indium-tin alloy two-phase metals:

[0152] Specifically, iron powder particles and gallium indium tin alloy (weight ratio of iron powder particles to gallium indium tin alloy is 1:7) are added to a 1M hydrochloric acid solution, and the volume ratio of hydrochloric acid to metal is 5:1. The mixture is stirred continuously at room temperature for 30 minutes until the iron powder particles are completely immersed in the gallium indium tin alloy. After washing off the hydrochloric acid, an iron-gallium indium tin alloy two-phase metal is obtained.

[0153] Preparation of polyvinyl alcohol solution:

[0154] Specifically, the steps for preparing a polyvinyl alcohol solution are as follows: dissolve 10 wt% of polyvinyl alcohol particles in deionized water, and continuously stir magnetically at 95°C for 1 hour until dissolved to obtain a polyvinyl alcohol solution.

[0155] Preparation of a two-phase metal-polyvinyl alcohol mixed solution:

[0156] The above-mentioned two-phase metal was mixed with a polyvinyl alcohol solution at a weight ratio of 3:2, and then stirred and sheared at 15,000 rpm for 5 minutes at room temperature using a hand-held homogenizer to obtain a mixed solution of iron-gallium indium tin alloy two-phase metal and polyvinyl alcohol.

[0157] dry:

[0158] The uniformly dispersed two-phase metal-polyvinyl alcohol mixture was heated to remove the good solvent.

[0159] Specifically, the obtained iron-gallium indium tin alloy two-phase metal-polyvinyl alcohol mixed solution was added to a polytetrafluoroethylene petri dish, and then placed in an environment of 60°C to remove the good solvent, thereby obtaining an iron-gallium indium tin alloy two-phase metal gel.

[0160] like Figure 11 As shown, the electronic conductivity of the iron-gallium-indium-tin alloy two-phase metal gel is 2.22 × 10⁻⁶. 6 S / m, toughness is 8.79 MJ / m 3 The Young's modulus is 3.84 MPa.

[0161] Preparation Example 4

[0162] Preparation of nickel-gallium-indium alloy two-phase metals:

[0163] Specifically, nickel powder particles and gallium indium alloy (the weight ratio of nickel powder particles to gallium indium alloy is 1:6) are added to a 1M hydrochloric acid solution, and the volume ratio of hydrochloric acid to metal is 5:1. The mixture is stirred continuously at room temperature for 30 minutes until the nickel powder particles are completely immersed in the gallium indium alloy. After washing off the hydrochloric acid, a nickel-gallium indium alloy two-phase metal is obtained.

[0164] Preparation of polyvinyl alcohol solution:

[0165] Specifically, the steps for preparing a polyvinyl alcohol solution are as follows: dissolve 10 wt% of polyvinyl alcohol particles in deionized water, and continuously stir magnetically at 95°C for 1 hour until dissolved to obtain a polyvinyl alcohol solution.

[0166] Preparation of a two-phase metal-polyvinyl alcohol mixed solution:

[0167] The above-mentioned two-phase metal was mixed with a polyvinyl alcohol solution at a weight ratio of 3:2, and then stirred and sheared at 15,000 rpm for 5 minutes at room temperature using a hand-held homogenizer to obtain a nickel-gallium-indium alloy two-phase metal-polyvinyl alcohol mixed solution.

[0168] dry:

[0169] The uniformly dispersed two-phase metal-polyvinyl alcohol mixture was heated to remove the good solvent.

[0170] Specifically, the obtained nickel-gallium indium alloy two-phase metal-polyvinyl alcohol mixed solution was added to a polytetrafluoroethylene petri dish, and then placed in an environment of 60°C to remove the good solvent, thus obtaining a nickel-gallium indium alloy two-phase metal gel.

[0171] like Figure 12 As shown, the electronic conductivity of the nickel-gallium-indium alloy two-phase metal gel is 2.15 × 10⁻⁶. 6 S / m, toughness is 14.6 MJ / m 3 The Young's modulus is 4.5 MPa.

[0172] Preparation Example 5

[0173] Preparation of iron-gallium-indium alloy two-phase metals:

[0174] Specifically, iron powder particles and gallium-indium alloy (weight ratio of iron powder particles to gallium-indium alloy is 1:12) are added to a 1M hydrochloric acid solution, and the volume ratio of hydrochloric acid to metal is 5:1. The mixture is stirred continuously at room temperature for 30 minutes until the iron powder particles are completely immersed in the gallium-indium alloy. After washing off the hydrochloric acid, an iron-gallium-indium alloy two-phase metal is obtained.

[0175] Preparation of polyvinyl alcohol solution:

[0176] Specifically, the steps for preparing a polyvinyl alcohol solution are as follows: dissolve 10 wt% of polyvinyl alcohol particles in deionized water, and continuously stir magnetically at 95°C for 1 hour until dissolved to obtain a polyvinyl alcohol solution.

[0177] Preparation of a two-phase metal-polyvinyl alcohol mixed solution:

[0178] The above-mentioned two-phase metal was mixed with a polyvinyl alcohol solution at a weight ratio of 3:2, and then stirred and sheared at 15,000 rpm for 5 minutes at room temperature using a hand-held homogenizer to obtain an iron-gallium indium alloy two-phase metal-polyvinyl alcohol mixed solution.

[0179] dry:

[0180] The uniformly dispersed two-phase metal-polyvinyl alcohol mixture was heated to remove the good solvent.

[0181] Specifically, the obtained iron-gallium indium alloy two-phase metal-polyvinyl alcohol mixed solution was added to a polytetrafluoroethylene petri dish, and then placed in an environment of 60°C to remove the good solvent, thereby obtaining an iron-gallium indium alloy two-phase metal gel.

[0182] like Figure 13 As shown, the electronic conductivity of the iron-gallium-indium alloy two-phase metal gel is 2.07 × 10⁻⁶. 6 S / m, toughness is 7.99MJ / m 3 The Young's modulus is 4.2 MPa.

[0183] Preparation Example 6

[0184] Preparation of nickel-gallium-indium alloy two-phase metals:

[0185] Specifically, nickel powder particles and gallium indium alloy (the weight ratio of nickel powder particles to gallium indium alloy is 1:11) are added to a 1M hydrochloric acid solution, and the volume ratio of hydrochloric acid to metal is 5:1. The mixture is stirred continuously at room temperature for 30 minutes until the nickel powder particles are completely immersed in the gallium indium alloy. After washing off the hydrochloric acid, a nickel-gallium indium alloy two-phase metal is obtained.

[0186] Preparation of polyvinyl alcohol solution:

[0187] Specifically, the steps for preparing a polyvinyl alcohol solution are as follows: dissolve 10 wt% of polyvinyl alcohol particles in deionized water, and continuously stir magnetically at 95°C for 1 hour until dissolved to obtain a polyvinyl alcohol solution.

[0188] Preparation of a two-phase metal-polyvinyl alcohol mixed solution:

[0189] The above-mentioned two-phase metal was mixed with a polyvinyl alcohol solution at a weight ratio of 3:2, and then stirred and sheared at 15,000 rpm for 5 minutes at room temperature using a hand-held homogenizer to obtain a nickel-gallium-indium alloy two-phase metal-polyvinyl alcohol mixed solution.

[0190] dry:

[0191] The uniformly dispersed two-phase metal-polyvinyl alcohol mixture was heated to remove the good solvent.

[0192] Specifically, the obtained nickel-gallium indium alloy two-phase metal-polyvinyl alcohol mixed solution was added to a polytetrafluoroethylene petri dish, and then placed in an environment of 60°C to remove the good solvent, thus obtaining a nickel-gallium indium alloy two-phase metal gel.

[0193] like Figure 14 As shown, the electronic conductivity of the nickel-gallium-indium alloy two-phase metal gel is 2.10 × 10⁻⁶. 6 S / m, toughness is 9.83 MJ / m 3 The Young's modulus is 4.9 MPa.

[0194] Preparation Example 7

[0195] Preparation of two-phase metals:

[0196] Preparation of copper-gallium-indium alloy two-phase metals;

[0197] Specifically, copper powder particles and gallium-indium alloy were added to a 4M sodium hydroxide solution at a weight ratio of 1:12. The mixture was continuously magnetically stirred at room temperature for 1 hour until the copper powder particles were infiltrated into the gallium-indium alloy. After washing off the sodium hydroxide, a copper-gallium-indium alloy two-phase metal was obtained.

[0198] Preparation of silver-gallium-indium alloy two-phase metals;

[0199] Specifically, silver powder particles and gallium-indium alloy were added to a 4M sodium hydroxide solution at a weight ratio of 1:12. The mixture was continuously magnetically stirred at room temperature for 1 hour until the silver powder particles were infiltrated into the gallium-indium alloy. After washing off the sodium hydroxide, a silver-gallium-indium alloy two-phase metal was obtained.

[0200] Preparation of gold-gallium-indium alloy two-phase metals;

[0201] Specifically, gold powder particles and gallium-indium alloy were added to a 4M sodium hydroxide solution at a weight ratio of 1:12. The mixture was continuously magnetically stirred at room temperature for 1 hour until the gold powder particles were infiltrated into the gallium-indium alloy. After washing off the sodium hydroxide, a gold-gallium-indium alloy two-phase metal was obtained.

[0202] Preparation of copper-gallium-indium-tin alloy two-phase metals;

[0203] Specifically, copper powder particles and gallium indium tin alloy were added to a 4M sodium hydroxide solution at a weight ratio of 1:12. The mixture was continuously magnetically stirred at room temperature for 1 hour until the copper powder particles were infiltrated into the gallium indium tin alloy. After washing off the sodium hydroxide, a copper-gallium indium tin alloy two-phase metal was obtained.

[0204] Preparation of silver-gallium-indium-tin alloy two-phase metal;

[0205] Specifically, silver powder particles and gallium indium tin alloy were added to a 4M sodium hydroxide solution at a weight ratio of 1:12. The mixture was continuously magnetically stirred at room temperature for 1 hour until the silver powder particles were infiltrated into the gallium indium tin alloy. After washing off the sodium hydroxide, a silver-gallium indium tin alloy two-phase metal was obtained.

[0206] Preparation of gold-gallium-indium-tin alloy two-phase metals;

[0207] Specifically, gold powder particles and gallium indium tin alloy were added to a 4M sodium hydroxide solution at a weight ratio of 1:12. The mixture was continuously magnetically stirred at room temperature for 1 hour until the gold powder particles were infiltrated into the gallium indium tin alloy. After washing off the sodium hydroxide, a gold-gallium indium tin alloy two-phase metal was obtained.

[0208] Preparation of iron-gallium-indium alloy two-phase metals;

[0209] Specifically, iron powder particles and gallium-indium alloy were added to a 4M sodium hydroxide solution at a weight ratio of 1:6. The mixture was stirred continuously at room temperature for 0.5 hours until the iron powder particles were infiltrated into the gallium-indium alloy. After washing off the sodium hydroxide, an iron-gallium-indium alloy two-phase metal was obtained.

[0210] Preparation of nickel-gallium-indium alloy two-phase metals;

[0211] Specifically, nickel powder particles and gallium-indium alloy were added to a 4M sodium hydroxide solution at a weight ratio of 1:6. The mixture was stirred continuously at room temperature for 0.5 hours until the nickel powder particles were infiltrated into the gallium-indium alloy. After washing off the sodium hydroxide, a nickel-gallium-indium alloy two-phase metal was obtained.

[0212] Preparation of NdFeB alloy-GaIn alloy two-phase metals;

[0213] Specifically, neodymium iron boron alloy particles and gallium indium alloy were added to a 4M sodium hydroxide solution at a weight ratio of 1:6. The mixture was stirred continuously at room temperature for 0.5 hours until the neodymium iron boron alloy particles were infiltrated into the gallium indium alloy. After washing off the sodium hydroxide, a neodymium iron boron alloy-gallium indium alloy two-phase metal was obtained.

[0214] Preparation of iron-gallium-indium-tin alloy two-phase metals;

[0215] Specifically, iron powder particles and gallium indium tin alloy are added to a 4M sodium hydroxide solution at a weight ratio of 1:6. The mixture is stirred continuously at room temperature for 0.5 hours until the copper powder particles are embedded in the gallium indium tin alloy. After washing off the sodium hydroxide, an iron-gallium indium tin alloy two-phase metal is obtained.

[0216] Preparation of nickel-gallium-indium-tin alloy two-phase metals;

[0217] Specifically, nickel powder particles and gallium indium tin alloy are added to a 4M sodium hydroxide solution at a weight ratio of 1:6. The mixture is stirred continuously at room temperature for 0.5 hours until the nickel powder particles are infiltrated into the gallium indium tin alloy. After washing off the sodium hydroxide, a nickel-gallium indium tin alloy two-phase metal is obtained.

[0218] Preparation of NdFeB alloy-GaInTin alloy two-phase metals;

[0219] Specifically, neodymium iron boron alloy particles and gallium indium tin alloy were added to a 4M sodium hydroxide solution at a weight ratio of 1:6. The mixture was stirred continuously at room temperature for 0.5 hours until the neodymium iron boron alloy particles were infiltrated into the gallium indium tin alloy. After washing off the sodium hydroxide, a neodymium iron boron alloy-gallium indium tin alloy two-phase metal was obtained.

[0220] Preparation of polyvinyl alcohol solution:

[0221] Specifically, the steps for preparing a polyvinyl alcohol solution are as follows: dissolve 10 wt% of polyvinyl alcohol particles in deionized water, and continuously stir magnetically at 95°C for 1 hour until dissolved to obtain a polyvinyl alcohol solution.

[0222] Preparation of a two-phase metal-polyvinyl alcohol mixed solution:

[0223] The copper-gallium indium alloy, silver-gallium indium alloy, gold-gallium indium alloy, copper-gallium indium tin alloy, silver-gallium indium tin alloy, and gold-gallium indium tin alloy were respectively mixed with a polyvinyl alcohol solution at a weight ratio of 13:7.

[0224] The above-mentioned iron-gallium indium alloy two-phase metal, nickel-gallium indium alloy two-phase metal, neodymium iron boron alloy-gallium indium alloy two-phase metal, iron-gallium indium tin alloy two-phase metal, nickel-gallium indium tin alloy two-phase metal, and neodymium iron boron alloy-gallium indium tin alloy two-phase metal were respectively mixed with polyvinyl alcohol solution at a weight ratio of 7:7.

[0225] Then, at room temperature, the mixture was stirred and sheared at 15,000 rpm for 5 minutes using a handheld homogenizer to obtain twelve different two-phase metal-polyvinyl alcohol mixed solutions.

[0226] dry:

[0227] The uniformly dispersed two-phase metal-polyvinyl alcohol mixture was heated to remove the good solvent.

[0228] Specifically, the obtained two-phase metal-polyvinyl alcohol mixed solutions of the twelve systems were added to polytetrafluoroethylene petri dishes, and then placed in an environment of 60°C to remove the good solvent, resulting in twelve two-phase metal gels.

[0229] Tests showed that the electronic conductivity, toughness, and Young's modulus of the two-phase metal gel prepared in Example 7 under alkaline conditions were comparable to those of the corresponding two-phase metal gel prepared in Example 1 under acidic conditions.

[0230] Preparation Example 8

[0231] Preparation of copper-gallium-indium alloy two-phase metals:

[0232] Specifically, copper powder particles with a particle size of 50-100 nm and gallium-indium alloy (the weight ratio of copper powder particles to gallium-indium alloy is 1:12) are added to a 1M hydrochloric acid solution. The volume ratio of hydrochloric acid to metal is about 5:1. The mixture is continuously magnetically stirred at room temperature for 1 hour until the copper powder particles are completely wetted inside the gallium-indium alloy. After washing off the hydrochloric acid, a copper-gallium-indium alloy two-phase metal with a particle size of 50-100 nm is obtained.

[0233] Specifically, copper powder particles with a diameter of 1 μm and gallium indium alloy (the weight ratio of copper powder particles to gallium indium alloy is 1:12) are added to a 1M hydrochloric acid solution. The volume ratio of hydrochloric acid to metal is approximately 5:1. The mixture is continuously magnetically stirred at room temperature for 1 hour until the copper powder particles are completely immersed in the gallium indium alloy. After washing off the hydrochloric acid, a copper-gallium indium alloy two-phase metal with a diameter of 1 μm is obtained.

[0234] Specifically, copper powder particles with a particle size of 5-10 μm and gallium indium alloy (the weight ratio of copper powder particles to gallium indium alloy is 1:12) are added to a 1M hydrochloric acid solution. The volume ratio of hydrochloric acid to metal is about 5:1. The mixture is continuously magnetically stirred at room temperature for 1 hour until the copper powder particles are completely immersed in the gallium indium alloy. After washing off the hydrochloric acid, a copper-gallium indium alloy two-phase metal with a particle size of 5-10 μm is obtained.

[0235] Preparation of polyvinyl alcohol solution:

[0236] Specifically, the steps for preparing a polyvinyl alcohol solution are as follows: dissolve 10 wt% of polyvinyl alcohol particles in deionized water, and continuously stir magnetically at 95°C for 1 hour until dissolved to obtain a polyvinyl alcohol solution.

[0237] Preparation of a two-phase metal-polyvinyl alcohol mixed solution:

[0238] The copper-gallium indium alloy binary metals of the above three particle sizes were mixed with polyvinyl alcohol solution at a weight ratio of 13:7. Then, the mixed solutions were stirred and sheared at 15000 rpm for 5 minutes at room temperature to obtain uniformly dispersed copper-gallium indium alloy binary metal-polyvinyl alcohol mixed solutions of the three particle sizes.

[0239] dry:

[0240] The uniformly dispersed two-phase metal-polyvinyl alcohol mixture was heated to remove the good solvent.

[0241] Specifically, the copper-gallium indium alloy two-phase metal-polyvinyl alcohol mixed solutions of the three particle sizes were added to polytetrafluoroethylene petri dishes, and then placed in an environment of 60°C to remove the good solvent, thus obtaining copper-gallium indium alloy two-phase metal gels of the three particle sizes.

[0242] like Figure 16 As shown, copper-gallium indium alloy two-phase metal gels of all three particle sizes exhibit excellent electronic conductivity and high toughness.

[0243] Specifically, the electronic conductivity of the prepared two-phase metal gel materials is greater than 2.00 × 10⁻⁶. 6 Both S / m and toughness are higher than 12 MJ·m 3 It achieves a balance between high electronic conductivity and high toughness.

[0244] In summary, the two-phase metals are interconnected throughout the material, forming a continuous phase, which provides excellent electronic pathways for the two-phase metal gel. The two-phase metal gel exhibits near-metallic electronic conductivity, with a minimum of 2.00 × 10⁻⁶. 6 S / m. The polyvinyl alcohol polymer network exhibits a continuous three-dimensional porous structure, providing excellent mechanical support for the two-phase metal gel and demonstrating outstanding toughness, reaching at least 7 MJ / m. 3 It also exhibits good flexibility, with a Young's modulus below 7 MPa. Hydrogen bonds exist between the polyvinyl alcohol polymer network and the two-phase metal, fixing the two-phase metal within the nanoscale dispersed polyvinyl alcohol polymer network and preventing leakage. Stable interfaces are formed between the components, resulting in a material that possesses excellent electronic conductivity, flexibility, and toughness.

[0245] The invention and its embodiments have been described above illustratively. This description is not restrictive, and the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. The accompanying drawings are only one embodiment of the invention, and the actual structure is not limited thereto. No reference numerals in the claims should limit the scope of the claims. Therefore, if a person skilled in the art is inspired by this description and designs a similar structure and embodiment without departing from the spirit of the invention, such design should fall within the scope of protection of this patent. Furthermore, the word "comprising" does not exclude other elements or steps, and the word "a" preceding an element does not exclude the inclusion of "a plurality" of that element. Multiple elements stated in the product claims may also be implemented by a single element through software or hardware. The terms "first," "second," etc., are used to indicate names and do not indicate any specific order.

Claims

1. A two-phase metal gel, characterized in that: It comprises a two-phase metal and polyvinyl alcohol, wherein the two-phase metal is dispersed in polyvinyl alcohol; The two-phase metal comprises rigid metal particles and flexible liquid metal; In the two-phase metal, the rigid metal particles have a size of 50 nm to 10 μm; In the two-phase metal, the mass ratio of rigid metal particles to flexible liquid metal is 1:(6~20); The mass ratio of the two-phase metal to polyvinyl alcohol is (30~70): 3; The binary metal gel does not contain a good solvent; The electronic conductivity of the two-phase metal gel is greater than or equal to 2.00 × 10⁻⁶. 6 S / m, toughness greater than or equal to 7 MJ·m 3 The value of Young's modulus is less than or equal to 7 MPa.

2. The two-phase metal gel according to claim 1, characterized in that, The preparation method of two-phase metal gel includes the following steps: Preparation of two-phase metals: Rigid metal particles and flexible liquid metals are mixed in an acidic or alkaline solution, stirred continuously, and then separated to obtain two-phase metals; Preparation of polyvinyl alcohol solution: Polyvinyl alcohol is dissolved in a good solvent to obtain a polyvinyl alcohol solution; Preparation of a two-phase metal-polyvinyl alcohol mixed solution: The two-phase metal is mixed and dispersed with the polyvinyl alcohol solution to obtain a two-phase metal-polyvinyl alcohol mixed solution; Drying: The two-phase metal-polyvinyl alcohol mixed solution is dried and the good solvent is removed in an environment of 25℃~80℃ to obtain a two-phase metal gel.

3. The two-phase metal gel according to claim 2, characterized in that: The rigid metal particles are selected from one or more of iron, nickel, copper, silver, gold, or neodymium iron boron alloys; The flexible liquid metal is selected from one or both of gallium indium alloy and gallium indium tin alloy.

4. The two-phase metal gel according to claim 3, characterized in that: The rigid metal particles are copper.

5. The two-phase metal gel according to claim 3, characterized in that: The two-phase metal is selected from one or more of the following: iron-gallium-indium alloy, nickel-gallium-indium alloy, copper-gallium-indium alloy, silver-gallium-indium alloy, gold-gallium-indium alloy, neodymium iron boron alloy-gallium-indium alloy, iron-gallium-indium tin alloy, nickel-gallium-indium tin alloy, copper-gallium-indium tin alloy, silver-gallium-indium tin alloy, gold-gallium-indium tin alloy, and neodymium iron boron alloy-gallium-indium tin alloy.

6. The two-phase metal gel according to claim 5, characterized in that: The mass ratio of the two-phase metal to the polyvinyl alcohol solution is (3~7):

3.

7. The two-phase metal gel according to claim 5, characterized in that: The flexible liquid metal is a gallium-indium alloy, wherein the mass ratio of gallium to indium in the gallium-indium alloy is 75.50:24.5; or The flexible liquid metal is a gallium indium tin alloy, wherein the mass ratio of gallium, indium, and tin in the gallium indium tin alloy is 68.50:21.50:10.

00.

8. The two-phase metal gel according to claim 5, characterized in that: In the step of preparing the two-phase metal, the concentration of the acidic or alkaline solution is 1~4M; In the step of preparing the polyvinyl alcohol solution, the good solvent is selected from one or both of deionized water and dimethyl sulfoxide; the concentration of the polyvinyl alcohol solution is 8 wt%-12 wt%. In the step of preparing the two-phase metal-polyvinyl alcohol mixed solution, the stirring speed for mixing and dispersing is 8000 rpm to 15000 rpm, and the stirring time is 5 to 15 min.

9. A flexible electronic product comprising the two-phase metal gel according to any one of claims 1 to 8.

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