Bifunctional device for photoelectric detection and energy storage and preparation method thereof

Abstract

The invention provides a bifunctional device for photoelectric detection and energy storage and a preparation method thereof.The bifunctional device comprises a negative electrode current collector layer, a working electrode layer, a hydrogel electrolyte layer and a counter electrode layer which are sequentially arranged, and the working electrode layer comprises a semiconductor material layer and a positive electrode material layer; one part of the hydrogel electrolyte layer is shielded by the counter electrode layer, and the other part, which is not shielded by the counter electrode layer, of the hydrogel electrolyte layer is used for allowing light to be detected to pass through. When the device is used for energy storage, the working electrode layer is used as a positive electrode, the counter electrode layer is used as a negative electrode, and the hydrogel electrolyte layer is used as a solid electrolyte; when photoelectric detection is carried out, the semiconductor material in the working electrode layer is used for capturing light to be detected and converting the light to be detected into an electric signal, and the hydrogel electrolyte layer is used as an electrolyte of the photoelectrochemical photoelectric detector, so that the dual functions of photoelectric detection and energy storage are realized through one device.

Description

Technical Field

[0001] The present application belongs to the technical field of photoelectric detection devices and energy storage devices, and specifically relates to a dual-function device for photoelectric detection and energy storage and a preparation method thereof. Background Art

[0002] Short-wave ultraviolet (UV) refers to electromagnetic waves with a wavelength between 200 and 280 nm. UV detectors have broad application prospects in environmental monitoring, UV communications, missile warning, and other fields, making research on them crucial. Currently, UV photodetectors can be categorized as photoconductive, photoelectrochemical (PEC), Schottky, pn junction, and pin (PIN) types. PEC UV photodetectors, among others, require no external power supply and feature a simple fabrication process, significantly reducing energy consumption.

[0003] With the continuous emergence of high-tech products, such as wearable smart electronics, the demand for miniaturized and micro-miniaturized energy storage devices is growing stronger. Aqueous zinc-ion batteries, due to their non-toxicity, non-combustibility, high specific capacity, and high abundance, have attracted widespread attention from researchers. Pure zinc is generally used as the negative electrode material for aqueous zinc-ion batteries, while the positive electrode material can be selected from vanadium-based compounds, manganese-based compounds, Prussian blue analogs, and conductive organic compounds.

[0004] People's simultaneous demand for ultraviolet photodetection and energy storage has promoted the development of dual-function devices of photodetection and energy storage. That is, how to achieve photodetection and energy storage on the same device at the same time is a technical problem that technicians in this field need to study and solve. Summary of the Invention

[0005] The technical problem solved by this application is: how to provide a dual-function device that can simultaneously realize photoelectric detection and energy storage.

[0006] The present application provides a dual-function device for photoelectric detection and energy storage, the dual-function device comprising a negative electrode current collector layer, a working electrode layer, a hydrogel electrolyte layer and a counter electrode layer arranged in sequence, the working electrode layer comprising a semiconductor material layer and a positive electrode material layer, a portion of the hydrogel electrolyte layer being blocked by the counter electrode layer, and the other portion of the hydrogel electrolyte layer not blocked by the counter electrode layer being used to pass the light to be detected.

[0007] Optionally, the semiconductor material layer is a nanocolumn structure layer, and the positive electrode material layer covers the upper end of the nanocolumn structure layer away from the negative electrode current collector layer.

[0008] Optionally, the nanocolumn structure layer includes at least one of a GaN nanocolumn layer and an AlGaN nanocolumn layer.

[0009] Optionally, the positive electrode material layer is a polyaniline material layer.

[0010] Optionally, the hydrogel electrolyte layer contains conductive ions.

[0011] Optionally, the counter electrode layer is a ring-shaped metal layer or an interdigital electrode.

[0012] Optionally, the counter electrode layer includes a metal layer and a transparent electrode, the metal layer covers a portion of the hydrogel electrolyte layer, the transparent electrode covers another portion of the hydrogel electrolyte layer and is used to pass the light to be detected.

[0013] Optionally, the material of the negative electrode current collector layer is a flexible conductive material.

[0014] The present application also provides a method for preparing a dual-function device for photoelectric detection and energy storage, the preparation method comprising:

[0015] A working electrode layer is prepared, wherein the working electrode layer comprises a semiconductor material layer and a positive electrode material layer;

[0016] Transferring the working electrode layer to the negative electrode current collector layer;

[0017] Forming a hydrogel electrolyte layer on the working electrode layer;

[0018] A counter electrode layer is formed on the hydrogel electrolyte layer.

[0019] Optionally, a nanorod structure layer is grown on the substrate as the semiconductor material layer;

[0020] peeling the nanorod structure layer from the substrate;

[0021] A positive electrode material layer is formed at one end of the nanocolumn structure layer.

[0022] The present application provides a dual-function device for photoelectric detection and energy storage and a method for preparing the same, which has the following technical effects:

[0023] When the device is performing energy storage, the working electrode layer serves as the positive electrode, the counter electrode layer serves as the negative electrode, and the hydrogel electrolyte layer serves as the solid electrolyte; when performing photoelectric detection, the semiconductor material in the working electrode layer is used to capture the light to be detected and convert it into an electrical signal, and the hydrogel electrolyte layer serves as the electrolyte of the photoelectrochemical photodetector, thus achieving the dual functions of photoelectric detection and energy storage through one device. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is a schematic diagram of a dual-function device for photodetection and energy storage according to one or more embodiments;

[0025] Figure 2 is another schematic diagram of a dual-function device for photodetection and energy storage according to one or more embodiments;

[0026] Figure 3 is a schematic diagram of a counter electrode layer according to one or more embodiments;

[0027] Figure 4 is another schematic diagram of a counter electrode layer according to one or more embodiments;

[0028] Figure 5 FIG. 4 is a schematic diagram of a process for manufacturing a semiconductor material layer according to one or more embodiments.

[0029] The correspondence between the reference numerals and component names is as follows:

[0030] 10-negative current collector layer, 20-working electrode layer, 21-semiconductor material layer, 22-positive electrode material layer, 30-hydrogel electrolyte layer, 40-counter electrode layer, 41-metal layer, 42-transparent electrode, 1-Si substrate, 2-AlN buffer layer, 3-GaN nanopillars, 4-AlGaN nanopillars, 5-AlN nanopillars, 6-AlGaN nanopillars. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical solutions and advantages of this application more clearly understood, the following further describes this application in detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit this application.

[0032] Before describing the various embodiments of the present application in detail, the technical concept of the present application is first briefly described: Currently, two independent devices are usually used for photoelectric detection and energy storage. To this end, the present application provides a dual-function device for photoelectric detection and energy storage, including a negative electrode current collector layer, a working electrode layer, a hydrogel electrolyte layer and a counter electrode layer stacked in sequence. When performing energy storage, the working electrode layer serves as the positive electrode, the counter electrode layer serves as the negative electrode, and the hydrogel electrolyte layer serves as a solid electrolyte; when performing photoelectric detection, the semiconductor material in the working electrode layer is used to capture the light to be detected and convert it into an electrical signal, and the hydrogel electrolyte layer serves as the electrolyte of the photoelectrochemical photodetector, thereby realizing photoelectric detection and energy storage through one device. The specific principles of the dual-function device for photoelectric detection and energy storage of the present application will be described below in conjunction with more embodiments.

[0033] Specifically, if Figure 1 and Figure 2 As shown, this embodiment provides a dual-function device for photoelectric detection and energy storage, which includes a negative electrode current collector layer 10, a working electrode layer 20, a hydrogel electrolyte layer 30 and a counter electrode layer 40 arranged in sequence. The working electrode layer 20 includes a semiconductor material layer 21 and a positive electrode material layer 22. A portion of the hydrogel electrolyte layer 30 is blocked by the counter electrode layer 40, and the other portion of the hydrogel electrolyte layer 30 that is not blocked by the counter electrode layer 40 is used to pass the light to be detected, that is, the counter electrode layer 40 has a light-transmitting structure, which can be a light-transmitting hole, a light-transmitting slit, or a light-transmitting portion, so that the light to be detected can enter the hydrogel electrolyte layer 30 and enter the semiconductor material layer 21 to achieve photoelectric detection.

[0034] In one or more embodiments, the semiconductor material layer 21 is a nanocolumn structure layer, and the positive electrode material layer 22 covers the upper end of the nanocolumn structure layer away from the negative electrode current collector layer 10. The semiconductor material layer 21 is a one-dimensional nanocolumn structure. With its ultra-high surface area to volume ratio, it can effectively improve the ability to capture photons and achieve a gain in photoelectric detection performance; at the same time, it can increase the contact area between the positive electrode material layer and the electrolyte, which has a gain effect on the energy storage function. Exemplarily, the semiconductor material layer 21 includes a stacked GaN nanocolumn layer and an AlGaN nanocolumn layer. The semiconductor material layer 21 can also be a separate GaN nanocolumn layer or a separate AlGaN nanocolumn layer. The use of two different nanocolumn layers is to facilitate the production of a nanocolumn structure layer.

[0035] For example, positive electrode material layer 22 is a polyaniline material layer (PANI). PANI has advantages such as good redox reversibility and low cost, and is a valuable positive electrode material for aqueous zinc-ion batteries. When the dual-function device operates as a photodetector, an organic-inorganic heterojunction is formed between the polyaniline material layer and the semiconductor material layer 21, inhibiting the recombination of photogenerated electron-hole pairs and enhancing the photoelectric response. During photodetection, the semiconductor material layer 21, to which the positive electrode material layer 22 is attached, serves as the working electrode; during energy storage, the polyaniline material layer serves as the positive electrode, integrating photodetection and energy storage functions in the same device.

[0036] In one or more embodiments, the hydrogel electrolyte layer 30 uses polyvinyl alcohol as a matrix. Polyvinyl alcohol-based hydrogels have high light transmittance. The hydrogel electrolyte layer 30 contains zinc ions, which serve as conductive ions. In other embodiments, other hydrogel electrolyte layers with high light transmittance and ionic conductivity may be used.

[0037] In one or more embodiments, Figure 3 and Figure 4As shown, the counter electrode layer 40 is an annular metal layer or an interdigitated electrode. Both the annular metal layer and the interdigitated electrode have light-transmitting slits, allowing the light to pass through and enter the hydrogel electrolyte layer 30 and the working electrode layer 20. In this case, the annular metal layer or the interdigitated electrode can serve as both the counter electrode for photoelectric detection and the negative electrode for energy storage, realizing the integration of photoelectric detection and energy storage functions in the same device.

[0038] In another embodiment, the counter electrode layer 40 includes a metal layer 41 and a transparent electrode 42. The metal layer 41 covers a portion of the hydrogel electrolyte layer 30, and the transparent electrode 42 covers another portion of the hydrogel electrolyte layer 30. The transparent electrode 42 is used to pass the light to be detected. In this case, the metal layer 41 serves as the negative electrode during energy storage, and the transparent electrode 42 serves as the counter electrode during photoelectric detection.

[0039] For example, the annular metal layer and the metal layer 41 may be made of zinc foil, and the interdigital electrodes may be galvanized interdigital electrodes.

[0040] Furthermore, the materials of the transparent electrode 42 and the negative electrode current collector layer 10 are preferably flexible conductive materials, such as any one or more of indium oxide-based films, zinc oxide-based films, tin oxide-based films, delafossite structure films, layered oxysulfide films, carbon nanotube films, graphene films, ultrathin metal films, metal grid films, and metal nanowire films. The use of flexible conductive materials is conducive to achieving device flexibility and broadening its application scenarios, such as application in smart wearable electronic products. In other embodiments, the negative electrode current collector layer 10 can also be any one or more of titanium foil, nickel foil, aluminum foil, stainless steel foil, carbon cloth, and graphite paper.

[0041] In the second embodiment, a method for preparing a dual-function device for photoelectric detection and energy storage includes the following steps:

[0042] Step S10: preparing a working electrode layer 20, wherein the working electrode layer 20 includes a semiconductor material layer 21 and a positive electrode material layer 22;

[0043] Step S20, transferring the working electrode layer 20 to the negative electrode current collector layer 10;

[0044] Step S30, forming a hydrogel electrolyte layer 30 on the working electrode layer 20;

[0045] Step S40 , forming a counter electrode layer 40 on the hydrogel electrolyte layer 30 .

[0046] The preparation steps of the working electrode layer 20 include the preparation steps of the semiconductor material layer 21 and the preparation steps of the positive electrode material layer 22 .

[0047] For example, Figure 5 As shown, the steps of manufacturing the semiconductor material layer 21 may include the following steps:

[0048] Step 1: Take a Si substrate 1 and clean the surface of the Si substrate 1 with acetone and ethanol solutions for a certain period of time.

[0049] Step 2: Place the cleaned Si substrate 1 into the growth chamber of the molecular beam epitaxy equipment to grow the epitaxial structure, and grow the AlN buffer layer 2, GaN nanopillars 3, AlGaN nanopillars 4, AlN nanopillars 5, and AlGaN nanopillars 6 in sequence. For example, grow a 3nm thick AlN buffer layer 2, and then grow a 200nm high GaN nanopillar 3 on the AlN buffer layer 2. Next, grow a 100nm high AlGaN nanopillar 4 on the GaN nanopillar 3, and then grow a 6nm high AlN nanopillar 5 thereon. Finally, grow a 180nm high AlGaN nanopillar 6 on the AlN nanopillar 5. Since AlN is easily corroded, the AlN nanopillar 5 is used to determine whether corrosion occurs on the surface of the nanopillar during subsequent electrochemical stripping, and the GaN nanopillar 3 is for better growth of the AlGaN nanopillar 4 in the future.

[0050] Step 3: The Si substrate 1 carrying the epitaxial structure is connected to a wire and placed in a 1 mol / L nitric acid solution for electrochemical stripping. The residual nitric acid solution on the epitaxial structure can be removed by soaking in deionized water for 2 hours, ultimately obtaining a nanopillar structure layer, i.e., a semiconductor material layer 21, which is composed of GaN nanopillars 3, AlGaN nanopillars 4, AlN nanopillars 5, and AlGaN nanopillars 6. It should be noted that the various parameters in the above-mentioned process for fabricating the nanopillar structure layer, i.e., the semiconductor material layer 21, are examples only and can be adjusted according to actual needs.

[0051] Furthermore, the positive electrode material layer 22 can be prepared in two different ways, namely based on chemical oxidation polymerization method and electrochemical deposition method. The preparation process is described below with a specific example, wherein the parameters in the example are only examples and can be adjusted according to actual needs.

[0052] The method for preparing the positive electrode material layer 22 based on the chemical oxidation polymerization method includes the following steps:

[0053] Step (1): In an ice-water bath, add aniline monomer to 30 ml of 0.2 mol / L HCl solution, stir for 10 min, then add 15 ml of 0.2 mol / L ammonium persulfate solution (APS) dropwise to make the molar ratio of aniline monomer to ammonium persulfate be 1:1, stir for 10 min, and obtain a reaction solution.

[0054] Step (2): The upper end of the semiconductor material layer 21 is brought into contact with the reaction solution prepared in step (1) by immersing the material in the reaction solution or by dripping the reaction solution onto the material. The reaction time is 24 hours and the temperature is controlled at 0°C.

[0055] Step (3): The semiconductor material layer 21 processed in step (2) is washed with deionized water and anhydrous ethanol and then vacuum dried. The drying temperature is controlled at 50° C. and the drying time is 10 h.

[0056] Thus, all steps of attaching the positive electrode material layer 22 to the surface of the semiconductor material layer 21 are completed. Here, the material of the positive electrode material layer 22 is PANI material.

[0057] The method for preparing the positive electrode material layer 22 based on the electrochemical deposition method includes the following steps:

[0058] Step (4): Add an appropriate amount of aniline monomer to 30 ml of 0.1 mol / L dilute sulfuric acid solution to obtain an electrolyte.

[0059] Step (5): Using the electrolyte prepared in step (4), in a three-electrode system of an electrochemical workstation, with the semiconductor material layer 21 as the working electrode, platinum as the counter electrode, and the Ag / AgCl electrode as the reference electrode, cyclic voltammetry is used to deposit the positive electrode material layer 22 on the surface of the semiconductor material layer 21.

[0060] Thus, all steps of attaching the positive electrode material layer 22 to the surface of the semiconductor material layer 21 are completed. Here, the material of the positive electrode material layer 22 is PANI material.

[0061] Furthermore, a hydrogel electrolyte was prepared to contain Zn 2+ Taking the preparation process of the hydrogel electrolyte as an example, the following two methods can be used. The parameters in each method are examples and can be changed according to actual needs.

[0062] Method 1 includes the following steps:

[0063] Step (11): 3 g of PVA was added to 20 ml of 1 mol / L ZnSO4 solution, and after magnetic stirring at 90°C for 30 min, the solution was transferred to a culture dish and allowed to stand at room temperature for 4 h.

[0064] Step (12): Place the solution prepared in step (11) in a refrigerator and freeze for 3 hours, then take it out and thaw it. Repeat the freezing-thawing process three times. Alternatively, directly drop the solution prepared in step (11) onto the working electrode layer 20 and dry it to form it. Thus, the Zn-containing 2+ Preparation of hydrogel electrolyte.

[0065] Method 2 includes the following steps:

[0066] Step (13): 3 g of PVA was added to 20 ml of deionized water, and after magnetic stirring at 90° C. for 30 min, the solution was transferred to a culture dish and allowed to stand at room temperature for 4 h.

[0067] Step (14): Place the solution prepared in step (13) in a refrigerator and freeze for 30 minutes, then take it out, drip a layer of 1.5 mol / L sodium citrate solution on the surface, and let it stand to form.

[0068] Step (15): Place the hydrogel formed in step (14) into a 1 mol / L ZnSO4 solution and soak for 15 minutes before taking it out. 2+ Preparation of hydrogel electrolyte.

[0069] In other embodiments, during the preparation of the hydrogel electrolyte, Zn(NO3)2, ZnCl2, Zn(ClO4)2, ZnF2, Zn(CF3SO3)2, Zn(TFSI)2 and Zn(CH3COO)2 can be used instead of the ZnSO4 solution.

[0070] Next, the working electrode layer 20 prepared in step S10 is transferred to the negative electrode current collector layer 10, and the hydrogel electrolyte prepared in the step is transferred to the working electrode layer 20 to form a hydrogel electrolyte layer 30. The material of the negative electrode current collector layer 10 can be indium tin oxide / polyethylene naphthalate, and the size of the negative electrode current collector layer 10 can be set according to actual needs, for example, it can be set to 1 cm×1 cm, 2 cm×1 cm, etc.

[0071] Furthermore, a counter electrode layer 40 is formed on the hydrogel electrolyte layer 30, and different forms of the counter electrode layer 40 can be used. In one or more embodiments, the counter electrode layer 40 adopts an annular metal layer or an interdigitated electrode. Both the annular metal layer and the interdigitated electrode have light-transmitting gaps, which can allow the light to be detected to pass through and enter the hydrogel electrolyte layer 30 and the working electrode layer 20. In another embodiment, the counter electrode layer 40 includes a metal layer 41 and a transparent electrode 42. The metal layer 41 covers a portion of the hydrogel electrolyte layer 30, and the transparent electrode 42 covers another portion of the hydrogel electrolyte layer 30 and is used to pass the light to be detected. After the counter electrode layer 40 is prepared in this step, the final dual-function device for photoelectric detection and energy storage is formed.

[0072] The above describes in detail the specific implementation methods of the present application. Although some embodiments have been shown and described, those skilled in the art should understand that these embodiments can be modified and improved without departing from the principles and spirit of the present application, the scope of which is defined by the claims and their equivalents. These modifications and improvements should also be within the scope of protection of the present application.

Claims

1. A dual-function device for photoelectric detection and energy storage, characterized in that: The bifunctional device includes a negative electrode current collector layer, a working electrode layer, a hydrogel electrolyte layer and a counter electrode layer arranged in sequence, the working electrode layer includes a semiconductor material layer and a positive electrode material layer, a portion of the hydrogel electrolyte layer is blocked by the counter electrode layer, and the other portion of the hydrogel electrolyte layer not blocked by the counter electrode layer is used to pass the light to be detected.

2. The dual-function device for photoelectric detection and energy storage according to claim 1, characterized in that: The semiconductor material layer is a nano-column structure layer, and the positive electrode material layer covers the upper end of the nano-column structure layer away from the negative electrode current collector layer.

3. The dual-function device for photoelectric detection and energy storage according to claim 2, characterized in that: The nano-column structure layer includes at least one of a GaN nano-column layer and an AlGaN nano-column layer.

4. The dual-function device for photoelectric detection and energy storage according to claim 2, characterized in that: The positive electrode material layer is a polyaniline material layer.

5. The dual-function device for photoelectric detection and energy storage according to claim 1, characterized in that: The hydrogel electrolyte layer contains conductive ions.

6. The dual-function device for photoelectric detection and energy storage according to claim 1, characterized in that: The counter electrode layer is a ring-shaped metal layer or an interdigital electrode.

7. The dual-function device for photoelectric detection and energy storage according to claim 1, characterized in that: The counter electrode layer includes a metal layer and a transparent electrode. The metal layer covers a portion of the hydrogel electrolyte layer. The transparent electrode covers another portion of the hydrogel electrolyte layer and is used to pass the light to be detected.

8. The dual-function device for photoelectric detection and energy storage according to claim 1, characterized in that: The negative electrode current collector layer is made of a flexible conductive material.

9. A method for preparing a dual-function device for photoelectric detection and energy storage according to any one of claims 1 to 8, characterized in that: The preparation method comprises: A working electrode layer is prepared, wherein the working electrode layer comprises a semiconductor material layer and a positive electrode material layer; Transferring the working electrode layer to the negative electrode current collector layer; Forming a hydrogel electrolyte layer on the working electrode layer; A counter electrode layer is formed on the hydrogel electrolyte layer.

10. The preparation method according to claim 9, characterized in that The method for preparing the working electrode layer comprises: Growing a nanorod structure layer on a substrate as a semiconductor material layer; peeling the nanorod structure layer from the substrate; A positive electrode material layer is formed at one end of the nanocolumn structure layer.

Images