Preparation Method and Application of a Plasmon-Effect-Enhanced Water Voltaic Device

Abstract

The present invention belongs to the technical field of green energy power generation, and discloses a preparation method and application of a water voltaic device with enhanced plasmonic effect. The preparation method includes: uniformly dispersing a conductive substrate material in a solvent and then treating it with a reducing agent to form a base material ink; using an additive and subtractive technique to prepare the base material ink into a three-dimensional structure with pores, and forming a stable substrate material through high-temperature treatment; immersing the stable substrate material in a plasmonic metal solution for a first preset time and then taking it out, then immersing it in a reducing agent solution for a second preset time and then taking it out, and using an additive and subtractive technique to cure it to form a water voltaic device with enhanced plasmonic effect. This preparation method constructs a three-dimensional bulk device with an interfacial pore structure through an additive and subtractive technique to improve the light absorption ability, and uses plasmonic nanoparticles to improve the light energy utilization rate, increase the device interface temperature, and provide additional carriers for the power generation process, which can improve the output power of the device.

Description

Technical Field

[0001] The present invention relates to a preparation method and application of a water-voltaic device with enhanced plasmonic effect, belonging to the technical field of green energy generation. Background Art

[0002] The collection and utilization of environmental thermal energy are important means for the development of new clean energy. Among them, the water-voltaic power generation technology uses the principle that a liquid absorbs environmental heat and generates charge accumulation at the interface evaporation, and has the advantages of environmental protection, self-driven, wide application scenarios, etc. At present, the materials of water-voltaic devices have developed to include conductors or semiconductor materials such as carbon materials and oxides; however, the performance of the devices constructed by these materials is generally low, especially the extremely low output current does not meet the requirements of actual production and life.

[0003] Through technologies such as volume heating and environmental convection control, the movement speed of the liquid in the water-voltaic device and the evaporation speed at the interface will be greatly increased, thereby increasing the output current of the device; however, these methods require additional equipment and electrical energy input, resulting in a significant reduction in production efficiency. Solar energy, as a clean energy, can act on the material surface in the form of light radiation to increase the evaporation interface temperature of the device, and then improve the evaporation rate to achieve the improvement of water-voltaic performance.

[0004] However, at present, the light absorbance of the interface of water-voltaic devices is limited, and the light energy cannot be fully utilized. Therefore, there is an urgent need for a technical means to improve the light energy utilization rate of the interface of water-voltaic devices and further improve the output performance. Summary of the Invention

[0005] The purpose of the present invention is to provide a preparation method and application of a water-voltaic device with enhanced plasmonic effect, which can solve the problems of insufficient light energy utilization rate of water-voltaic devices and low water-voltaic output current performance.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] In the first aspect, the present invention provides a preparation method of a water-voltaic device with enhanced plasmonic effect, including:

[0008] Uniformly disperse the conductive substrate material in a solvent and then treat it with a reducing agent to form a substrate ink;

[0009] Use additive and subtractive techniques to prepare the substrate ink into a three-dimensional structure with pores, and form a stable substrate material through high-temperature treatment;

[0010] Immerse the stable substrate material in a plasmonic metal solution for a first preset time and then take it out, then immerse it in a reducing agent solution for a second preset time and then take it out, and use additive and subtractive techniques to cure it to form a water-voltaic device with enhanced plasmonic effect.

[0011] In combination with the first aspect, further, the conductive substrate material includes one or more combinations of carbon materials, oxides, and organic conductive materials.

[0012] In combination with the first aspect, further, the solvent used to disperse the conductive substrate material is acetone or ethanol.

[0013] In combination with the first aspect, further, the reducing agent includes one or more combinations of sodium borohydride, ascorbic acid, oxalic acid, lithium aluminum hydride, ammonium sulfide, and the concentration of the reducing agent is 0.001 mmol / L to 5 mol / L.

[0014] In combination with the first aspect, further, the additive and subtractive manufacturing technology includes 3D printing technology, investment casting technology, or freeze casting technology.

[0015] In combination with the first aspect, further, the temperature range of the high-temperature treatment is 200°C to 1400°C, the heating rate of the high-temperature treatment is 0.1°C / min to 10°C / min, and the time of the high-temperature treatment is 0.5 h to 10 h.

[0016] In combination with the first aspect, further, the plasmonic metal solution includes one or more combinations of metal salt solutions and metal coordination acid solutions, and the concentration of the plasmonic metal solution is 0.001 mmol / L to 10 mol / L.

[0017] In the second aspect, the present invention provides an application of a plasmonic effect-enhanced hydrovoltaic device prepared by the preparation method described in any item of the first aspect in the field of power generation. One end of the hydrovoltaic device is placed in a liquid, the liquid evaporates through the hydrovoltaic device under the application environment conditions, an electric potential is generated at both ends of the hydrovoltaic device, and a current is generated inside the hydrovoltaic device.

[0018] In combination with the second aspect, further, the liquid used to place the hydrovoltaic device includes one or more combinations of organic liquids, deionized water, aqueous single-salt solutions, and aqueous multi-salt solutions.

[0019] In combination with the second aspect, further, the application environment conditions include no-light conditions and light conditions, and the light intensity is 0.01 kW / m 2 ~100 kW / m 2 .

[0020] Compared with the prior art, the beneficial effects of the present invention are:

[0021] The preparation method of the plasmonic effect-enhanced hydrovoltaic device provided by the present invention uses an additive-subtractive technology to prepare a three-dimensional structure with a pore-shaped light-trapping structure on its surface, which can not only improve the light absorption ability but also facilitate liquid flow and evaporation; the introduction of plasmonic nanoparticles further improves the light absorption through the plasmon resonance effect and increases the carrier concentration of the device, enabling a significant breakthrough in the hydrovoltaic current performance. Description of the Drawings

[0022] Figure 1 It is a schematic diagram for testing the plasmonic effect-enhanced hydrovoltaic device provided by an embodiment of the present invention;

[0023] Figure 2 It is a comparison chart of absorbance with and without gold nanoparticles provided by an embodiment of the present invention;

[0024] Figure 3 It is a schematic diagram of the structure of a cubic hydrovoltaic device with a porous interface and a composite of copper nanoparticles and graphene carbon nanotubes provided by an embodiment of the present invention;

[0025] Figure 4 It is a schematic diagram of the relationship between the size of copper particles and the treatment time with sodium borohydride provided by an embodiment of the present invention. Detailed Embodiments

[0026] The technical solutions of the present application will be further described in detail below in conjunction with the specific embodiments.

[0027] The embodiments of the present application will be described in detail below. The examples of the embodiments are shown in the drawings, where the same or similar reference numerals represent the same or similar elements or elements with the same or similar functions from beginning to end. The embodiments described below by referring to the drawings are exemplary and are only used to explain the present application and should not be construed as a limitation to the present application. Without conflict, the embodiments of the present application and the technical features in the embodiments can be combined with each other.

[0028] The embodiments of the present application provide a preparation method of a plasmonic effect-enhanced hydrovoltaic device, including:

[0029] Uniformly disperse the conductive substrate material in a solvent and then treat it with a reducing agent to form a substrate ink;

[0030] Use an additive-subtractive technology to prepare the substrate ink into a three-dimensional structure with pores and form a stable substrate material through high-temperature treatment;

[0031] Immerse the stable substrate material in a plasmonic metal solution for a first preset time and then take it out, then immerse it in a reducing agent solution for a second preset time and take it out, and use an additive-subtractive technology to cure it to form a plasmonic effect-enhanced hydrovoltaic device.

[0032] The preparation method of the plasmonic effect-enhanced hydrovoltaic device provided by the embodiment of the present application uses the additive and subtractive manufacturing technology to prepare a three-dimensional structure with a pore-shaped light-trapping structure on the surface, which can not only improve the light absorption ability, but also facilitate liquid flow and evaporation; the introduction of plasmonic nanoparticles further improves light absorption through the plasmon resonance effect and increases the carrier concentration of the device, enabling a significant breakthrough in the hydrovoltaic current performance.

[0033] In this embodiment, the conductive substrate material includes one or more combinations of carbon materials, oxides, and organic conductive materials; the solvent used to disperse the conductive substrate material is acetone or ethanol; the reducing agent includes one or more combinations of sodium borohydride, ascorbic acid, oxalic acid, lithium aluminum hydride, ammonium sulfide, and the concentration of the reducing agent is 0.001 mmol / L to 5 mol / L.

[0034] In this embodiment, the additive and subtractive manufacturing technology includes 3D printing technology, investment casting technology, or freeze casting technology; the temperature range of the high-temperature treatment is 200°C to 1400°C, the heating rate of the high-temperature treatment is 0.1°C / min to 10°C / min, and the time of the high-temperature treatment is 0.5 h to 10 h.

[0035] In this embodiment, the plasmonic metal solution includes one or more combinations of metal salt solutions and metal coordination acid solutions, and the concentration of the plasmonic metal solution is 0.001 mmol / L to 10 mol / L.

[0036] In a possible embodiment, the preparation method of the plasmonic effect-enhanced hydrovoltaic device specifically includes the following steps:

[0037] Step A1, preparation of the base material ink: Prepare a dispersion of carbon black oxide with a concentration of 0.08 mol / mL in acetone, measure 50 mL of the carbon black oxide dispersion, add 20 mL of a sodium borohydride solution with a concentration of 2.6 mol / L, stir evenly, place it in an oven at 70°C for 2 h, centrifuge and remove the upper clear liquid, collect the lower turbid liquid and stir for 2 h, and obtain carbon black oxide ink after suction filtration.

[0038] Step A2, preparation of the substrate material: Use an inkjet direct writing 3D printer to inject the carbon black oxide ink prepared in Step A1, and print and prepare a cube with a size of 26 mm 3 ~38 mm 3 The printing rate is 30 mm / s, and the extrusion air pressure is 20 kPa; place the cube in the refrigerator and freeze it for 48 h, then transfer it to a freeze dryer and freeze-dry it for 48 h to obtain a carbon black oxide cube evaporator with a pore interface.

[0039] Step A3, Plasmonic Nanoparticle Growth: Immerse the carbon black cubic evaporator with a pore interface prepared in Step A2 in a 1 mol / L chloroauric acid solution for 2 h. After taking it out, transfer it to a 1 mol / L ammonium sulfide solution and soak for 5 min. After taking it out, freeze it in liquid nitrogen for 2 h, and then transfer it to a freeze dryer for freeze-drying for 24 h to obtain a gold nanoparticle-carbon black cubic water voltaic device with a pore interface.

[0040] Step A4, Water Voltaic Power Generation Application Test: As Figure 1 shown, cover the carbon paste on the glass slide, bond the water voltaic device prepared in Step A3 with the carbon paste, and lead it out with a copper wire as the lower electrode. Place the whole in a glass petri dish with a diameter of 5 cm, inject 20 mL of a sodium chloride solution with a concentration of 0.01 mol / L, wrap the copper electrode with carbon cloth and place it on the upper layer of the water voltaic device as the upper electrode; connect the upper and lower electrodes to a current source meter, and apply simulated light with an intensity of 12 kW / m 2 above the device, then the application test can be carried out, and an output voltage of 0.38 V and an output current of 400 μA can be measured.

[0041] The comparison of the absorbance with and without gold nanoparticles is as Figure 2 shown. It can be seen from Figure 2 that the absorbance of the water voltaic device has increased from 95% before loading to 96%. This indicates that the water voltaic device loaded with gold nanoparticles has enhanced the light absorption ability for the full spectrum, and can utilize solar irradiation more efficiently to improve the power generation performance.

[0042] In a possible embodiment, the preparation method of the water voltaic device with enhanced plasmonic effect specifically includes the following steps:

[0043] Step B1, Preparation of Substrate Ink: Prepare a dispersion of carbon black in acetone with a concentration of 0.2 mol / mL. Measure 50 mL of the carbon black dispersion, add 5 g of silicon oxide powder, stir evenly, add 1 mL of a sodium borohydride solution with a concentration of 3.1 mol / L, stir and then let it stand to obtain a silicon oxide-carbon black composite ink.

[0044] Step B2, Preparation of Substrate Material: Use the model casting method to inject the silicon oxide-carbon black composite ink prepared in Step B1, and cast a conical structure with a height of 0.8 cm. Place the conical structure in the refrigerator and freeze it for 48 h, then transfer it to a freeze dryer for freeze-drying for 48 h. After demolding, obtain a silicon oxide-carbon black composite cubic evaporator with a pore interface.

[0045] Step B3, Plasmonic nanoion growth: Immerse the silica carbon black composite cubic evaporator with a pore interface prepared in Step B2 in a 1 mmol / L silver chloride solution for 2 h. After taking it out, transfer it to a 1.5 mol / L ammonium sulfide solution and soak for 5 min. After taking it out, place it in liquid nitrogen for freezing for 2 h, and then transfer it to a freeze dryer for freeze-drying for 24 h to obtain a cubic water volt generator device composed of silver nanoparticle silica carbon black composite with a pore interface.

[0046] Step B4, Water volt power generation application test: Cover the carbon glue on the glass slide, bond the water volt generator device prepared in Step B3 with the carbon glue, and lead it out with a copper wire as the lower electrode. Place the whole in a glass petri dish with a diameter of 5 cm, inject 20 mL of a sodium chloride solution with a concentration of 0.01 mol / L, and wrap the copper electrode with carbon cloth and place it on the upper layer of the water volt device as the upper electrode; Connect the upper and lower electrodes to a current source meter, and apply simulated light with 12 kW / m 2 above the device, then the application test can be carried out, and an output voltage of 0.6 V and an output current of 600 μA can be measured.

[0047] In a possible embodiment, the preparation method of the water volt generator device with enhanced plasmonic effect specifically includes the following steps:

[0048] Step C1, Preparation of substrate ink: Prepare a dispersion of oxidized carbon black in acetone with a concentration of 0.08 mol / mL. Measure 50 mL of the oxidized carbon black dispersion, add 20 mL of a sodium borohydride solution with a concentration of 2.6 mol / L, stir evenly, place it in an oven at 70 °C for 2 h, centrifuge and remove the upper clear liquid, collect the lower turbid liquid and stir for 2 h, and obtain oxidized carbon black ink after filtration.

[0049] Step C2, Preparation of substrate material: Pour the oxidized carbon black ink prepared in Step C1 into a block, and use laser engraving to construct a grid-like cubic structure to obtain an oxidized carbon black cubic evaporator.

[0050] Step C3, Plasmonic nanoion growth: Immerse the oxidized carbon black cubic evaporator prepared in Step C2 in a 1 mmol / L copper sulfate solution for 1 h. After taking it out, transfer it to a 5 mol / L ammonium sulfide solution and soak for 3 min. After taking it out, place it in liquid nitrogen for freezing for 2 h, and then transfer it to a freeze dryer for freeze-drying for 24 h to obtain a cubic water volt generator device composed of copper nanoparticle graphene carbon nanotube composite with a pore interface as shown in Figure 3 the figure.

[0051] Step C4, Application test of hydrovoltaic power generation: Cover the carbon glue on the glass slide, bond the hydrovoltaic device prepared in Step A3 with the carbon glue, and lead out with a copper wire as the lower electrode. Place the whole in a glass petri dish with a diameter of 5 cm, inject 20 mL of sodium chloride solution with a concentration of 0.01 mol / L, and wrap the copper electrode with carbon cloth and place it on the upper layer of the hydrovoltaic device as the upper electrode; connect the upper and lower electrodes to the current source meter, and apply simulated light with an intensity of 12 kW / m 2 to conduct the application test, and an output voltage of 0.3 V and an output current of 210 μA can be measured.

[0052] The relationship between the size of copper nanoparticles and the treatment time of sodium borohydride is as Figure 4 shown. It can be seen from Figure 4 that as the soaking time of the evaporator in the copper sulfate solution increases, the size of the copper nanoparticles gradually increases, which reflects the characteristic that the technical solution of this application can adjust the size of the nanoparticles.

[0053] The embodiment of the present application provides an application of a hydrovoltaic device with enhanced plasmonic effect prepared by the preparation method of a hydrovoltaic device with enhanced plasmonic effect provided in any embodiment of the present application in the field of power generation. One end of the hydrovoltaic device is placed in a liquid, the liquid evaporates through the hydrovoltaic device under the application environment conditions, electric potential is generated at both ends of the hydrovoltaic device, and current is generated inside the hydrovoltaic device.

[0054] In this embodiment, the liquid used to place the hydrovoltaic device includes one or more combinations of organic liquids, deionized water, aqueous single-salt solutions, and aqueous multi-salt solutions; the application environment conditions include no-light conditions and light conditions, and the light intensity is 0.01 kW / m 2 ~100 kW / m 2 .

[0055] The above are only the preferred embodiments of the present application. It should be noted that for those of ordinary skill in the art, without departing from the technical principle of the present application, several improvements and deformations can be made, and these improvements and deformations should also be regarded as the protection scope of the present application.

Claims

1. A preparation method of a water voltaic device with enhanced plasmonic effect, characterized in that, Including: Uniformly disperse the conductive substrate material in a solvent and then treat it with a reducing agent to form a substrate ink; Use additive and subtractive techniques to prepare the substrate ink into a three-dimensional structure with pores, and form a stable substrate material through high-temperature treatment; Immerse the stable substrate material in a plasmonic metal solution for a first preset time and then take it out, then immerse it in a reducing agent solution for a second preset time and then take it out, and use additive and subtractive techniques to cure and form a water voltaic device with enhanced plasmonic effect.

2. The preparation method of the plasmonic effect-enhanced hydrovoltaic device according to claim 1, characterized in that, The conductive substrate material includes one or more combinations of carbon materials, oxides, and organic conductive materials.

3. The preparation method of the plasmon effect enhanced hydrovoltaic device according to claim 1, characterized in that, The solvent used to disperse the conductive substrate material is acetone or ethanol.

4. The preparation method of the plasmon effect-enhanced hydrovoltaic device according to claim 1, characterized in that, The reducing agent includes one or more combinations of sodium borohydride, ascorbic acid, oxalic acid, lithium aluminum hydride, ammonium sulfide, and the concentration of the reducing agent is 0.001 mmol / L to 5 mol / L.

5. The preparation method of the plasmon effect enhanced hydrovoltaic device according to claim 1, characterized in that, The additive and subtractive techniques include 3D printing technology, investment casting technology, or freeze casting technology.

6. The preparation method of the plasmon effect-enhanced hydrovoltaic device according to claim 1, characterized in that, The temperature range of the high-temperature treatment is 200°C to 1400°C, the heating rate of the high-temperature treatment is 0.1°C / min to 10°C / min, and the time of the high-temperature treatment is 0.5 h to 10 h.

7. The preparation method of the plasmonic effect-enhanced hydrovoltaic device according to claim 1, characterized in that, The plasmonic metal solution includes one or more combinations of metal salt solutions and metal coordination acid solutions, and the concentration of the plasmonic metal solution is 0.001 mmol / L to 10 mol / L.

8. Use of a plasmonic effect-enhanced hydrovoltaic device prepared by the preparation method according to any one of claims 1 to 7 in the field of power generation, characterized in that, One end of the water voltaic device is placed in a liquid, the liquid evaporates through the water voltaic device under the application environmental conditions, an electric potential is generated at both ends of the water voltaic device, and a current is generated inside the water voltaic device.

9. Use of the plasmon effect-enhanced hydrovoltaic device according to claim 8 in the field of power generation, characterized in that, The liquid used to place the water voltaic device includes one or more combinations of organic liquids, deionized water, aqueous single salt solutions, and aqueous multi-salt solutions.

10. Application of the plasmon effect-enhanced hydrovoltaic device according to claim 8 in the field of power generation, characterized in that, The application environmental conditions include no-light conditions and light conditions, and the light intensity corresponding to the light conditions is 0.01 kW / m 2 ~100 kW / m 2 .

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