Preparation method and application of photoelectric gel based on liquid metal

Abstract

The invention relates to a preparation method and application of photoelectric gel based on liquid metal. In the preparation process of the gel, excellent electrical properties and mechanical properties of the liquid metal nanoparticles and photoelectric properties of an oxide film formed on the surfaces of the liquid metal nanoparticles are utilized, the hydrogel is used as a polymer network, the liquid metal nanoparticles are captured in the gelling process, and a flexible photoelectric device is constructed. Due to the good compatibility of the liquid metal nanoparticles and the hydrogel, the device always has excellent and stable photoelectric detection performance in the states of stretching, bending and the like. According to the preparation method and application of the photoelectric gel based on the liquid metal, the photoelectric gel has the advantages of being simple in process, low in cost, excellent in performance, stable in structure and the like, and has wide application prospects in the field of flexible photoelectric devices.

Description

Technical field:

[0001] The invention relates to the field of hydrogels and flexible optoelectronic devices, and in particular to a preparation method and application of a photoelectric gel based on liquid metal. Background technology:

[0002] Flexible electronic devices have been intensively studied due to their stable performance during deformation processes such as stretching, and polymer colloids are widely used to prepare elastomers in flexible devices due to their special structure and properties. Among them, hydrogel is a hydrophilic polymer network whose porous structure can be combined with rigid fillers with different stimulus responses to achieve diverse functions in various fields, such as wearable devices and biomedicine. However, due to the poor mechanical properties of rigid fillers, the gels currently under study have defects such as poor toughness, no self-healing properties, and low tensile strength, which greatly limit their application scenarios. Therefore, the development of rigid fillers with superior functionality and good mechanical properties is an effective way to improve the performance of gels and expand their application scenarios.

[0003] Liquid metal is a metal material that is in liquid state at room temperature. It has high conductivity, high fluidity, and high ductility. Its nanoparticles can be obtained through ultrasonic treatment. At the same time, the oxide film coated on the surface of the particles has good photoelectric properties. Therefore, liquid metal nanoparticles are suitable as rigid fillers for the preparation of functional flexible gels. During the polymer gelation process, the superior mechanical properties of liquid metal nanoparticles enable them to be well combined with the elastomer structure, while the oxide film coated on its surface gives the gel excellent photoelectric detection performance. The prepared flexible and stretchable photoelectric gel has both excellent mechanical and photoelectric properties, and has broad application prospects in wearable devices, biomedicine and other fields. Summary of the invention:

[0004] The present invention aims to provide a preparation method and application of a photoelectric gel based on liquid metal.

[0005] To achieve the above object, the present invention adopts the following technical solution:

[0006] The present invention provides a preparation method and application of a liquid metal-based photoelectric gel, comprising the following steps:

[0007] 1) Place pure Ga (liquid at room temperature), pure In, and pure Sn metal particles in a wide-mouth bottle according to a certain mass percentage, heat them with an alcohol lamp to completely melt them, and obtain a GaInSn alloy after cooling;

[0008] 2) taking equal masses of GaInSn alloy and adding them to anhydrous ethanol and a transition metal salt solution respectively, and obtaining an alcohol solution containing GaInSn nanoparticles wrapped by a gallium oxide film (hereinafter referred to as gallium oxide particles) and a transition metal salt solution containing GaInSn nanoparticles wrapped by a metal oxide film (hereinafter referred to as transition metal oxide particles) respectively by probe ultrasound;

[0009] 3) The gallium oxide particles in the alcohol solution obtained in step 2) and the transition metal oxide particles in the transition metal salt solution are respectively filtered and washed twice with deionized water, and then dried to obtain gallium oxide particles and transition metal oxide particles;

[0010] 4) Add the gallium oxide particles obtained in step 3) to a beaker, add ethylene glycol, sodium tetraborate, and polyvinyl alcohol powder, stir on a heated stirring platform, and obtain a photoelectric gel based on gallium oxide particles (hereinafter referred to as Hydrogel-1) after cooling; add the transition metal oxide particles obtained in step 3) to a beaker, add ethylene glycol, sodium tetraborate, and polyvinyl alcohol powder, stir on a heated stirring platform, and obtain a photoelectric gel based on transition metal oxide particles (hereinafter referred to as Hydrogel-2) after cooling; add the gallium oxide particles and transition metal oxide particles obtained in step 3) to a beaker, add ethylene glycol, sodium tetraborate, and polyvinyl alcohol powder, stir on a heated stirring platform, and obtain a photoelectric gel based on gallium oxide particles and transition metal oxide particles (hereinafter referred to as Hydrogel-3) after cooling; according to the same steps, only ethylene glycol, sodium tetraborate, and polyvinyl alcohol powder are added, stirred on a heated stirring platform, and cooled to obtain a photoelectric gel without liquid metal nanoparticles (hereinafter referred to as Hydrogel) as a control;

[0011] 5) The photoelectric gel obtained in step 4) is tested by an electrochemical system under different light intensities to obtain the photoelectric properties of the photoelectric gel.

[0012] Preferably according to the present invention, in step 1), the mass ratio of pure Ga, pure In and pure Sn is 6:2:1; the heating temperature of the alcohol lamp is about 200° C., the heating time is 30 min; and the cooling time is 3 h.

[0013] Preferably, according to the present invention, in step 2), the volume of anhydrous ethanol is 30 mL, the volume and concentration of the transition metal salt solution are 30 mL and 0.5 mol / L respectively, the mass of the GaInSn alloy added to the anhydrous ethanol and the transition metal salt solution respectively is 3 g, and the time and power of the probe ultrasound are 30 min and 60% respectively.

[0014] Preferably, in step 3), the deionized water is used for filtration and cleaning for 30 minutes, the drying temperature is 60° C., and the drying time is 12 hours.

[0015] Preferably according to the present invention, in step 4), the mass of the gallium oxide particles is 200 mg, the mass of the transition metal oxide particles is 200 mg, the volume of ethylene glycol added is 0.8 mL, the mass of sodium tetraborate is 160 mg, the mass of polyvinyl alcohol is 100 mg, the heating temperature is 100° C., the stirring time is 20 min, and the cooling time is 3 h.

[0016] According to the preferred embodiment of the present invention, in step 5), the light intensity is 200, 300, 400, 500 mW / cm 2 All equipment and raw materials used in the method of the present invention are commercially available products.

[0017] Based on the above technical solution, it can be seen that the present invention has the following advantages:

[0018] (1) The present invention has found through research that, compared with the traditional methods of preparing two-dimensional materials with complicated processes and high costs, the chemical properties of liquid metal oxide films are utilized to conveniently prepare functional metal oxide films through electrical replacement reactions. While ensuring the high conductivity of nanoparticles, their photoelectric properties are enhanced, thus broadening the application scope of liquid metals.

[0019] (2) As a polymer network with a highly elastic and highly stretchable structure, the gel can self-heal and recover in a short time under stretching conditions. The good compatibility between liquid metal nanoparticles and hydrogels enables the device to always have excellent and stable photoelectric detection performance under stretching conditions. Description of the drawings:

[0020] In order to more clearly illustrate the specific implementation of the present invention or the technical solution in the prior art, the following is a brief introduction to the drawings required for use in the specific implementation or the prior art description:

[0021] Figure 1 This is a scanning electron microscope (SEM) image of the ultrasonically prepared liquid metal nanoparticles of the present invention.

[0022] Figure 2 This is a physical picture of the photoelectric gel prepared by the present invention.

[0023] Figure 3 It is a comparison chart of the light detection performance of four photoelectric gels, namely Hydrogel, Hydrogel-1, Hydrogel-2 and Hydrogel-3, prepared by the present invention.

[0024] Figure 4 The Hydrogel-3 photoelectric gel prepared by the present invention has a high power density of 200, 300, 400 and 500 mW / cm 2 Graph of light detection performance versus light intensity. Specific implementation method:

[0025] The present invention is further described in detail below by specific examples, wherein the raw materials are all industrial products. The examples are only used to explain the present invention and cannot be construed as limiting the present invention. Changes or modifications to the equivalent forms of the present invention by those skilled in the art also fall within the scope defined by the appended claims of the present application.

[0026] Embodiment 1:

[0027] The prepared four photoelectric gels, Hydrogel, Hydrogel-1, Hydrogel-2 and Hydrogel-3, were connected to the electrochemical system for light response test. A 350W xenon lamp was used as the illumination light source. The light intensity was 500mW / cm 2 Under the condition of bias voltage of 0V, the test is carried out by alternating illumination and shading with a cycle of 10s. Figure 3 As shown, under the same test conditions, the light detection performance of the three photoelectric gels, Hydrogel-1, Hydrogel-2 and Hydrogel-3, was improved from 4mV / cm to 5.8mV / cm compared with the Hydrogel control gel, with a performance improvement of 45%, proving that the addition of gallium oxide particles and transition metal oxide particles enhanced the photoelectric performance of the gel.

[0028] Embodiment 2:

[0029] The prepared Hydrogel-3 photoelectric gel was connected to the electrochemical system for light response test. A 350W xenon lamp was used as the illumination light source. The light intensity was 200, 300, 400, and 500 mW / cm 2 Test under the following conditions. Figure 4 As shown, as the light intensity increases from 200 to 500 mW / cm 2 The photovoltage of the photoelectric gel increased from 11mV / cm to 19mV / cm, proving that the gel has a strong sensitivity to changes in light intensity.

Claims

1. A preparation method and application of a liquid metal-based photoelectric gel, comprising the following steps: 1) Place pure Ga (liquid at room temperature), pure In, and pure Sn metal particles in a wide-mouth bottle according to a certain mass percentage, heat them with an alcohol lamp to completely melt them, and obtain a GaInSn alloy after cooling; 2) taking equal masses of GaInSn alloy and adding them to anhydrous ethanol and a transition metal salt solution respectively, and obtaining an alcohol solution containing GaInSn nanoparticles wrapped by a gallium oxide film (hereinafter referred to as gallium oxide particles) and a transition metal salt solution containing GaInSn nanoparticles wrapped by a metal oxide film (hereinafter referred to as transition metal oxide particles) respectively by probe ultrasound; 3) The gallium oxide particles in the alcohol solution obtained in step 2) and the transition metal oxide particles in the transition metal salt solution are respectively filtered and washed twice with deionized water, and then dried to obtain gallium oxide particles and transition metal oxide particles; 4) Add the gallium oxide particles obtained in step 3) to a beaker, add ethylene glycol, sodium tetraborate, and polyvinyl alcohol powder, stir on a heated stirring platform, and obtain a photoelectric gel based on gallium oxide particles (hereinafter referred to as Hydrogel-1) after cooling; add the transition metal oxide particles obtained in step 3) to a beaker, add ethylene glycol, sodium tetraborate, and polyvinyl alcohol powder, stir on a heated stirring platform, and obtain a photoelectric gel based on transition metal oxide particles (hereinafter referred to as Hydrogel-2) after cooling; add the gallium oxide particles and transition metal oxide particles obtained in step 3) to a beaker, add ethylene glycol, sodium tetraborate, and polyvinyl alcohol powder, stir on a heated stirring platform, and obtain a photoelectric gel based on gallium oxide particles and transition metal oxide particles (hereinafter referred to as Hydrogel-3) after cooling; according to the same steps, only ethylene glycol, sodium tetraborate, and polyvinyl alcohol powder are added, stirred on a heated stirring platform, and cooled to obtain an electric gel without liquid metal nanoparticles (hereinafter referred to as Hydrogel) as a control; 5) The photoelectric gel (Hydrogel, Hydrogel-1, Hydrogel-2, Hydrogel-3) obtained in step 4) is tested by an electrochemical system under different light intensities to obtain the photoelectric properties of the photoelectric gel.

2. The preparation method and application of a liquid metal-based photoelectric gel according to claim 1, characterized in that: In step 1), the mass percentages of pure Ga, pure In and pure Sn are 6:2:1 respectively; the heating temperature of the alcohol lamp is about 200° C., the heating time is 30 min; and the cooling time is 3 h.

3. The preparation method and application of a liquid metal-based photoelectric gel according to claim 1, characterized in that: In step 2), the volume of anhydrous ethanol is 30 mL, the volume and concentration of the transition metal salt solution are 30 mL and 0.5 mol / L respectively, the mass of the GaInSn alloy added to the anhydrous ethanol and the transition metal salt solution is 3 g respectively, and the time and power of the probe ultrasound are 30 min and 60% respectively.

4. The preparation method and application of a liquid metal-based photoelectric gel according to claim 1, characterized in that: In step 3), the deionized water is used for filtration and cleaning for 30 minutes, the drying temperature is 60° C., and the drying time is 12 hours.

5. The preparation method and application of a liquid metal-based photoelectric gel according to claim 1, characterized in that: In step 4), the mass of gallium oxide particles is 200 mg, the mass of transition metal oxide particles is 200 mg, the volume of ethylene glycol added is 0.8 mL, the mass of sodium tetraborate is 160 mg, the mass of polyvinyl alcohol is 100 mg, the heating temperature is 100° C., the stirring time is 20 min, and the cooling time is 3 h.

6. The preparation method and application of liquid metal-based photoelectric gel according to claim 1, characterized in that: In step 5), the light intensity is 200, 300, 400, 500 mW / cm 2 .

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