Patterned water photovoltaic power generation device and preparation method thereof

Abstract

The invention relates to a patterned water photovoltaic power generation device and a preparation method thereof, and belongs to the technical field of water photovoltaic power generation devices. The preparation method comprises the following steps: S1, dissolving a complexing agent, zinc salt and reducing sugar in water to obtain a zinc precursor solution; s2, printing the zinc precursor solution on the surface of a substrate through printing equipment to form a pattern, and carrying out thermocuring and annealing to obtain a patterned zinc oxide film; and S3, transferring the patterned zinc oxide thin film to the surface of the flexible substrate, and then manufacturing an electrode on the patterned zinc oxide thin film to obtain the patterned water photovoltaic power generation device. The patterned photovoltaic power generation device has a voltage output of more than 9 V, and has device stability for continuous 7 hours.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrovoltaic devices, and particularly relates to a patterned hydrovoltaic device and a preparation method thereof. Background Art

[0002] The water resources on the earth are extremely rich, accounting for 71% of the earth's surface. Water contains huge energy in various forms such as rivers, tides, raindrops, etc. Among them, raindrops contain huge energy. The annual global rainfall of nearly 50 trillion tons can be converted into about 10 19 J of energy, which is sufficient to meet the global annual electricity demand and is a highly potential sustainable energy source. Therefore, how to effectively utilize the energy generated by the low-frequency and disordered raindrop movement has become a research hotspot in recent years (Nat. Rev. Mater. 2024; Nature 2020, 578, 392).

[0003] In recent years, inorganic hydrovoltaic devices have attracted much attention from scientists due to their excellent stability, various material selections, portability, and huge power generation potential (Nature 2020, 578, 550; Sci. Adv. 2023, 9, eadi2993). In 2014, Yin et al. found that a voltage of several millivolts could be generated by moving a droplet on graphene (Nat. Nanotech. 2014, 9, 378). With the continuous development of inorganic hydrovoltaic devices, Adha Sukma Aj et al. generated an output voltage greater than 5V in 2020 by moving a sodium chloride solution on molybdenum disulfide material (Nano Energy 2020, 68, 104370). Currently, the output voltage of inorganic hydrovoltaic devices is still relatively low, and it is difficult to meet the power supply requirements for devices under actual conditions.

[0004] Currently, the vast majority of inorganic hydrovoltaic devices are prepared based on thin film structures, and the thin film has a strong shielding effect, which will lead to a weakening of the solid-liquid interaction and a reduction in the Debye length. Therefore, it is difficult for the electric double layer to accommodate more charges (Science 2021, 372, 1327; NatEnergy 2021, 6, 419), ultimately resulting in a lower voltage output and stability of the device (Nature 2016, 529, 185; Nat. Nanotechnol. 2018, 13, 1109; Chem. Soc. Rev. 2022, 51, 4902). Therefore, exploring the surface structure and weakening the shielding effect to enhance the solid-liquid interaction and achieve significant charge transfer is crucial for improving the performance of hydrovoltaic devices. Summary of the Invention

[0005] To solve the above technical problems, the present invention provides a patterned hydrovoltaic device and a preparation method thereof, and the patterned hydrovoltaic device has excellent output voltage and stability.

[0006] The first object of the present invention is to provide a preparation method of a patterned hydrovoltaic device, comprising the following steps:

[0007] S1. Dissolve a complexing agent, a zinc salt and a reducing sugar in water to obtain a zinc precursor solution;

[0008] S2. Through a printing device, print the zinc precursor solution described in S1 on the surface of a substrate to form a pattern, and obtain a patterned zinc oxide thin film through thermal curing and annealing;

[0009] S3. Transfer the patterned zinc oxide thin film described in S2 to the surface of a flexible substrate, and then fabricate electrodes on the patterned zinc oxide thin film to obtain the patterned hydrovoltaic device.

[0010] In an embodiment of the present invention, in S1, the mass ratio of the complexing agent, the zinc salt and the reducing sugar is 1:(0.5-3):(0.1-2).

[0011] In an embodiment of the present invention, in S1, the complexing agent is selected from polyethyleneimine or its derivatives; the zinc salt is selected from one or more of zinc nitrate, zinc acetate, zinc sulfate and zinc chloride; the reducing sugar is selected from one or more of maltose, chitosan and glucose.

[0012] Furthermore, the molecular weight of the complexing agent is 10,000-20,000 to regulate the viscosity of the zinc precursor solution.

[0013] In an embodiment of the present invention, in S1, the viscosity of the zinc precursor solution is 25 Pa s-70 Pa s.

[0014] In an embodiment of the present invention, in S2, the parameters of the printing device are: the air pressure is 3 kg / cm 2 -6 kg / cm 2 , and the speed is 1 mm / s-5 mm / s.

[0015] In an embodiment of the present invention, in S2, the number of meandering lines of the pattern is 7-13, the line width is 100 μm-350 μm, the line spacing is 115 μm-390 μm, and the line length is 5 mm-25 mm.

[0016] In an embodiment of the present invention, in S2, the temperature of the thermal curing is 80°C-120°C, and the time is 1 min-3 min. The complexing agent and the reducing sugar will be cured and crosslinked under this condition to ensure the stability of the pattern during the annealing process.

[0017] In one embodiment of the present invention, in S2, the annealing temperature is 600°C - 900°C, and the time is 2h - 5h. Annealing under these conditions can form a dense and continuous patterned zinc oxide thin film.

[0018] In one embodiment of the present invention, the substrate is selected from a silicon substrate and / or a quartz substrate; the flexible substrate is selected from a PMMA substrate and / or PDMS.

[0019] Furthermore, the substrate is a PDMS substrate. Using a flexible PDMS substrate can avoid mechanical damage that is prone to occur on a rigid substrate, thereby reducing the impact on the device life; at the same time, the patterned design of the device avoids the strong shielding effect of the thin film device, thus avoiding problems that affect stability.

[0020] In one embodiment of the present invention, in S2, before use, the substrate needs to be pretreated with piranha solution at 140°C - 160°C for 25min - 35min, and then the substrate is placed in an ultrasonic cleaner and cleaned three times and dried with a nitrogen gun. Piranha solution has strong oxidizing properties and can thoroughly remove almost all organic substances on the substrate. Moreover, the surface of the substrate treated with it will carry hydroxyl groups and is thus highly hydrophilic, which can be used for subsequent modification.

[0021] The second object of the present invention is to provide a patterned water voltaic device prepared by the described method.

[0022] The technical solution of the present invention has the following advantages compared with the prior art:

[0023] (1) The complexing agent in the zinc precursor solution of the present invention contains abundant amino groups that can coordinate with zinc salts to solve problems such as uneven dispersion and nozzle clogging that occur in most inks due to the easy aggregation of inorganic nanoparticles caused by van der Waals forces; reducing sugars can ensure the stability of the pattern during annealing. Using the Maillard reaction, crosslinking and curing are formed during the thermal curing process. This makes the zinc precursor solution exhibit uniform and stable characteristics; at the same time, after annealing, the patterned zinc oxide structure also exhibits continuous and dense characteristics.

[0024] (2) The patterned water voltaic device of the present invention contains a patterned zinc oxide thin film structure; this patterned zinc oxide meandering line structure is prepared from a unique precursor of complexing agent - zinc ion - reducing sugar through steps such as printing - thermal curing - annealing; this enables the patterned water voltaic device to have a voltage output exceeding 9V and a device stability of 7 consecutive hours.

[0025] (3) When the preparation method of the present invention forms an electric double layer upon solid-liquid contact, ZnO, as a polar material, can form a built-in electric field, promoting charge separation and enhancing the performance output of the watervoltaic device. Compared with traditional thin-film devices, the patterned watervoltaic generator device increases the three-dimensional surface of solid-liquid contact (expanding the contact surface on the side of the material). In addition, the patterned structure weakens the depolarization field inside the thin film, strengthens the orientation of electric dipoles near the thin film surface, further increases the local electric field of zinc oxide to enhance the solid-liquid interaction, thereby achieving high-voltage output in the patterned watervoltaic generator device.

[0026] (4) The preparation method of the present invention has a simple process flow, reducing costs while improving production efficiency. In addition, it can also mass-produce zinc oxide pattern arrays by printing. The prepared large-area patterned watervoltaic generator devices can power watches, making multi-scenario applications possible. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to make the content of the present invention easier to be clearly understood, the following further details the present invention according to specific embodiments of the present invention in combination with the accompanying drawings, where:

[0028] Figure 1 is the process flow chart of the patterned watervoltaic generator device of the present invention;

[0029] Figure 2 is the viscosity test chart of the zinc precursor solution in Test Example 1 of the present invention;

[0030] Figure 3 is the schematic diagram of the thermal curing mechanism of the patterned zinc precursor in Test Example 2 of the present invention; where a is the curing crosslinking mechanism of maltose and polyethyleneimine, and b is the N-1s XPS spectrum of the zinc precursor before and after curing;

[0031] Figure 4 is the thermogravimetric change chart of the thermal decomposition of the zinc precursor in Test Example 3 of the present invention;

[0032] Figure 5 is the XRD spectrum of the patterned zinc oxide thin film and the zinc oxide thin film in Test Example 4 of the present invention;

[0033] Figure 6 is the influence of different printing parameters on the pattern line width in Test Example 5 of the present invention; where a is the line width change chart and b is the SEM image;

[0034] Figure 7 is the ζ potential test chart of the patterned watervoltaic generator device in Test Example 6 of the present invention;

[0035] Figure 8 is the theoretical calculation (a) and quantitative analysis (b) of the surface potential distribution of the watervoltaic generator device in Test Example 7 of the present invention;

[0036] Figure 9 Transfer charge amount and electric double - layer capacitance test chart of the water - voltaic generator device for Test Example 8 of the present invention;

[0037] Figure 10 Influence of different patterns and different printing parameters on the output performance of the water - voltaic generator device for Test Example 9 of the present invention; among them, a is the voltage - time curve of the output performance of the patterned zinc - oxide water - voltaic device in Example 1, b is the output performance of the patterned zinc - oxide water - voltaic device under different numbers of meandering lines, c is the output performance of the patterned zinc - oxide water - voltaic device under different line widths, and d is the output performance of the patterned zinc - oxide water - voltaic device under different line lengths;

[0038] Figure 11 Contact angle of the water - voltaic generator device with different line widths for Test Example 9 of the present invention;

[0039] Figure 12 Voltage - time curve of the patterned water - voltaic generator device for Test Example 10 of the present invention;

[0040] Figure 13 Process flow chart of the large - area patterned water - voltaic generator device for Test Example 11 of the present invention;

[0041] Figure 14 Parallel current and series voltage test chart of the large - area patterned water - voltaic generator device for Test Example 11 of the present invention;

[0042] Figure 15 Practical application diagram of the large - area patterned water - voltaic generator device for Test Example 11 of the present invention;

[0043] Figure 16 Data chart of the performance recovery after heating of the large - area patterned water - voltaic generator device for Test Example 11 of the present invention. Detailed implementation manners

[0044] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, so that those skilled in the art can better understand the present invention and be able to implement it. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. It should be understood that the specific embodiments are only used to explain the present invention, but the exemplified embodiments do not limit the present invention.

[0045] In the present invention, unless otherwise specified, the technical and scientific terms used in the present invention have the same meanings as those commonly understood by those skilled in the technical field to which the present invention belongs.

[0046] In the present invention, unless otherwise specified, the term "and / or" used in the present invention includes any and all combinations of one or more of the related listed items.

[0047] In the present invention, unless otherwise specified, the experimental methods used in the embodiments of the present invention are all conventional methods without special instructions, and the materials, reagents, etc. used can be obtained from commercial channels without special instructions.

[0048] In the present invention, unless otherwise specified, the piranha solution used in the embodiments of the present invention is a mixture of concentrated sulfuric acid and 30% hydrogen peroxide (7:3).

[0049] Example 1

[0050] Refer to Figure 1 As shown, the patterned water-based power generation device of the present invention and its preparation method specifically include the following steps:

[0051] S1. Preparation of zinc precursor solution:

[0052] S11. Preparation of mixed solution: Weigh 10 g of zinc nitrate (Zn(NO 3 ) 2 ) and 5 g of polyethyleneimine (PEI) in 50 mL of deionized water, place it on a magnetic stirrer and stir to mix evenly, add a small amount of hydrochloric acid to adjust the pH of the solution to about 7, and continue to stir for 4 h at room temperature to obtain a transparent and uniform solution; then transfer the transparent and uniform solution to an Amicon device equipped with a 10 kPa ultrafiltration membrane, add ultrapure water to a volume of 150 mL, close the ultrafiltration device and use nitrogen pressure to filter to remove all unbound cations / anions, repeat ultrafiltration until 50 mL is obtained to get the mixed solution;

[0053] S12. Preparation of maltose solution: Weigh 2.5 g of maltose and dissolve it in 10 mL of ultrapure water, stir until the solution is clear and uniform to obtain the maltose solution;

[0054] S13. Preparation of zinc precursor solution: Mix the mixed solution and the maltose solution evenly, stir for 4 h to obtain a clear and uniform solution, and then place the solution on a heating magnetic stirrer at 90 °C to concentrate 60 mL of the solution to 20 mL to obtain a brown zinc precursor solution.

[0055] S2. Preparation of patterned zinc oxide thin film:

[0056] S21. Pretreatment of substrate: Treat the silicon and sapphire substrates with piranha solution, react at 150 °C for 30 min, after piranha treatment, place the substrates in an ultrasonic cleaner and clean three times and dry with a nitrogen gun to obtain the pretreated substrates;

[0057] S22. Printing of the patterned zinc precursor: Load the zinc precursor solution into a printing syringe, place the whole in a direct ink writing device, design a pattern (the number of zigzag lines is 11, the line width is 200 μm, the line spacing is 280 μm, the line length is 15 mm) (the printing area is 5×15 mm 2 ) and design the printing parameters (the air pressure is 4 kg / cm 2 , the speed is 4 mm / s), and print the zinc precursor solution on the surface of the pretreated substrate to form a pattern, obtaining a patterned zinc precursor;

[0058] S23. Patterned zinc oxide thin film: The patterned zinc precursor is thermally cured at 100 °C, and then placed in a tube furnace and annealed in air at 600 °C for 2 h, and naturally cooled to room temperature, obtaining a patterned zinc oxide thin film with a thickness of about 1 μm.

[0059] S3. Preparation of the patterned water voltaic device:

[0060] S31. Transfer of the patterned zinc oxide thin film: Use a polydimethylsiloxane (PDMS) solution (curing agent: main agent = 1:9) (Sylgard 184), spin-coat and cover it on the patterned zinc oxide thin film, heat and cure it at 80 °C, and transfer the patterned zinc oxide thin film from the substrate to a flexible substrate with a thickness of about 200 μm;

[0061] S32. Preparation of the electrodes: Use conductive silver paste to make horizontal two electrodes on the patterned zinc oxide thin film, obtaining a patterned water voltaic device.

[0062] Comparative Example 1

[0063] Basically the same as Example 1, except that the zinc oxide thin film is not patterned, obtaining a water voltaic device.

[0064] Test Example 1

[0065] Based on Example 1, the viscosity of the zinc precursor solution was tested, and the results are as Figure 2 shown. It can be seen from Figure 2 that the zinc precursor solution has a certain fluidity and the viscosity is about 35 Pa s.

[0066] Test Example 2

[0067] Based on Example 1, the principle of the thermal curing of the zinc precursor is as Figure 3 shown. It can be seen from Figure 3 a that the hydroxyl group in maltose undergoes thermal cross-linking with the amino group in polyethyleneimine to form a tertiary amine group and an amide group, thereby realizing thermal curing cross-linking and preparing the required zinc precursor pattern; it can be seen from Figure 3 b that after heating and curing, -R in the zinc precursor 2The NH group (398.8 eV) decreased from 84.93% to 13.11%, while the tertiary amine R 3 N group (400.5 eV) showed a significant increase, from 15.07% to 84.93%.

[0068] Test Example 3

[0069] Based on Example 1, the weight change of the zinc precursor was monitored after the annealing process, and the results are as Figure 4 shown. From Figure 4 it can be seen that both PEI and the maltose-PEI copolymer can be completely decomposed in air. When the temperature rises to 100 °C, the weight begins to decrease due to the gradual dehydration of maltose. When the temperature is higher than 300 °C, maltose and PEI begin to pyrolyze, and when the temperature reaches 600 °C, the material growth is basically completed without residue.

[0070] Test Example 4

[0071] Based on Example 1 and Comparative Example 1, XRD characterization was performed on the patterned zinc oxide thin film and the zinc oxide thin film, and the results are as Figure 5 shown. From Figure 5 it can be seen that the patterned zinc oxide thin film and the zinc oxide thin film have consistent good crystallinity, ensuring the intrinsic properties and preparation consistency of the zinc oxide material, which is convenient for subsequent comparison.

[0072] Test Example 5

[0073] Based on Example 1, the influence of different printing parameters (different air pressures and different speeds) on the pattern line width was explored, and the results are as Figure 6 shown. From Figure 6 it can be seen that by adjusting the printing air pressure and printing speed, patterns with line widths of 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, and 350 μm can be obtained respectively after annealing at 600 °C.

[0074] Test Example 6

[0075] Based on Example 1, the surface potential of the patterned water voltaic device in Example 1 was tested by the surface potential analysis mode of a Malvern particle size analyzer, and the results are as Figure 7 shown. From Figure 7 it can be seen that the ZnO material has a Zeta potential between -31.6 mV and -34.9 mV in aqueous solution.

[0076] Test Example 7

[0077] Based on Example 1 and Comparative Example 1, the surface potential distribution of the water voltaic device was simulated and quantitatively simulated and analyzed using COMSOL software, and the results are as Figure 8 shown. FromFigure 8 It can be seen that the three-dimensional surface area of water contact with the material is increased in the water-voltaic device of Example 1. Compared with the water-voltaic device of Comparative Example 1, not only the horizontal surface of the material contacts with water, but also the contact surfaces of both sides of the material with water are increased. Both sides of the patterned zinc oxide thin film structure are completely exposed to water, presenting a negative surface potential, which is consistent with the results of Test Example 6. From Figure 8 b It can be seen that compared with the water-voltaic device of Comparative Example 1, the three-dimensional patterned water-voltaic device of Example 1 strengthens the orientation of electric dipoles near the film surface by weakening the depolarization field inside the film, promotes the increase of the surface potential of the horizontal plane, and at the same time expands the contact surface between the side of the material and water.

[0078] Test Example 8

[0079] Based on Example 1 and Comparative Example 1, the double-layer capacitance and charge transfer amount of the water-voltaic device were tested, and the results are as Figure 9 shown. It can be seen from the CV test of the two and the data analysis of the current i and the scan rate v under the same voltage condition that the water-voltaic device of Example 1 shows a larger pseudocapacitance C. At the same time, the water-voltaic device of Example 1 (181 nC) has a higher transferred charge compared with the water-voltaic device of Comparative Example 1 (6.5 nC). Therefore, from the comprehensive analysis, compared with Comparative Example 1, the water-voltaic device of Example 1 has a larger double-layer capacitance and more charge transfer occurs. It shows that the water-voltaic device of Example 1 shows better solid-liquid interaction, which is characterized by a large amount of charge accumulated in the EDL, thus promoting a larger charge transfer. It shows that the three-dimensional synergistic effect of the patterned zinc oxide thin film structure can significantly enhance the local electric field, strengthen the solid-liquid interaction, thereby effectively improving the charge directional transfer ability, and finally realizing the high-performance output of the device.

[0080] Test Example 9

[0081] Based on Example 1, the influence of different patterns (the number of meandering lines is 1, 3, 5, 7, 9, 11, 13 respectively, the line width is 100 μm - 350 μm, and the line length is 5 mm - 25 mm) on the output performance of the water-voltaic device was explored, and the results are as Figure 10 shown.

[0082] From Figure 10 a It can be seen that the voltage output of the patterned zinc oxide water-voltaic device in Example 1 exceeds 9V.

[0083] From Figure 10It can be seen that as the number of meandering lines of the patterned zinc oxide thin film increases, the contact area between the droplet and the material also expands, resulting in an increase in the transferred charge amount and a gradual enhancement of the voltage output. When the number of meandering lines reaches 13, although the volume of the droplet remains unchanged, the continuous increase in the device area makes it difficult for the droplet to completely cover the patterned surface. This incomplete coverage imposes an external load on the device, leading to a slight decline in the output performance.

[0084] From Figure 10 It can be seen from c that as the line width increases, the voltage output of the patterned zinc oxide hydrovoltaic device increases. This is because the voltage output is generated by charge transfer, and the relationship can be expressed by Equation 1, where C represents the pseudo-capacitance per unit area of zinc oxide - solution, Q represents the transferred charge amount, and V represents the voltage output. The calculation method of Q is shown in Equation 2, where n represents the number of charges and e represents the elementary charge. The calculation method of C is shown in Equation 3, where ε r is the dielectric constant, k is the electrostatic constant, C is mainly related to the solid-liquid contact area S and the distance d between the positive and negative charge layers, and d represents the narrow gap between these charge layers. As the solid-liquid contact area increases, the capacitance C 1 also increases. The relationship between the total capacitance (C total ) and the sub-capacitance (C 1 ) is shown in Equation 4. Therefore, as the solid-liquid contact area increases, C total will decrease, while the transferable charge Q will increase.

[0085] V = Q / C (1)

[0086] Q = n·e (2)

[0087] C = ε r S / 4πkd (3)

[0088]

[0089] However, the contact angles of hydrovoltaic devices with different line widths (100 μm - 350 μm) were measured, and the results are as Figure 11 shown. From Figure 11 it can be seen that as the line width increases from 100 μm to 350 μm, the change in the contact angle is always <1°; it can be seen that the solid-liquid contact area does not change significantly. Therefore, the capacitance C total remains basically unchanged, while the transferred charge amount increases significantly. This is because the patterned hydrovoltaic device increases the three-dimensional surface of the solid-liquid contact (expands the contact surface on the side of the material), thereby improving the voltage output. When the line width exceeds 200 μm, the horizontal surface of the material increases, resulting in an increase in the solid-liquid contact area and attracting more charges to the material surface. This leads to a stronger interaction between the charged particles and an increase in the screening charge effect of the EDL, resulting in a decrease in the voltage output.

[0090] From Figure 10 Figure 10 It can be seen that as the wire length increases, the increase in the contact area leads to an increase in voltage output. At the same time, the charged particles absorbed on the solid-liquid interface also increase, which will increase the shielding effect, thereby reducing the voltage output and causing a slight decline in device performance. This shows that the generation of voltage directly depends on the solid-liquid contact.

[0091] Test Example 10

[0092] Based on Example 1 and Comparative Example 1, the stability of the hydrovoltaic device was tested. The voltage-time curve results of the hydrovoltaic device are as Figure 12 shown. From Figure 12 Figure 12 It can be seen that compared with Comparative Example 1, the hydrovoltaic device in Example 1 can provide a voltage output of 9V for 7 hours, demonstrating its feasibility, reliability, and stability.

[0093] Test Example 11

[0094] Referring to Figure 13 shown, multiple pattern arrays (the integrable area of the array is 6×8.5 cm 2 , containing a total of 20 units) were printed on the surface of a 15×15 cm 2 pretreated substrate, and then a large-area patterned hydrovoltaic device was prepared using the process of Example 1. Figure 13 Figure 13 The image of a single device weighing 0.11 g is also shown. This lightweight and flexible device is convenient for carrying and integration.

[0095] Here, a large-area integrable ZnO pattern array was used, and silver conductive paint was used for series connection (5) and parallel connection (7) to facilitate circuit self-assembly. The parallel current and series voltage of the device are as Figure 14 shown. From Figure 14 Figure 14 It can be seen that 5 series-connected ZnO pattern arrays can generate a voltage of 20V during power generation, while 7 parallel-connected ZnO pattern arrays can generate a current of 160 nA. This shows that this large-area series-parallel structure allows for a linear increase in voltage and current.

[0096] In power generation applications, a stable and consistent voltage is crucial for long-term operation. Referring to Figure 15 shown, through optimized connection, an 8×12.5 cm 2 integrated device (containing 28 ZnO pattern arrays) connected in parallel can continuously power a watch. Due to its long-term stability, this device is an ideal choice for powering low-power devices that operate for a long time, reducing the dependence on batteries under rainy conditions. Due to its long-term stability, a large-area integrated device (28 ZnO pattern arrays) can provide a stable output for 90 min under high-density droplet conditions when powering low-power devices.

[0097] When the device performance degrades, heat the device (heat for 30 minutes at 30 °C), and the performance recovery after heating is as Figure 16 shown. It can be seen from Figure 16 this that heating can remove surface moisture and enable it to resume power supply for low-power devices. This indicates that the patterned hydrovoltaic generator device can restore its performance through heating with long-term stability and high cycle utilization rate.

[0098] Therefore, by increasing the integration area and combining series-parallel configurations, this patterned hydrovoltaic generator device is expected to provide a lasting power source for more electrical devices in various scenarios.

[0099] Obviously, the above embodiments are merely examples given for clear illustration and are not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to enumerate all the implementation manners here. And the obvious changes or modifications derived therefrom are still within the protection scope of this invention.

Claims

1. A method for preparing a patterned hydrovoltaic power generation device, characterized in that: The following steps are involved: S1, dissolving a complexing agent, a zinc salt and a reducing sugar in water to obtain a zinc precursor solution; S2, printing the zinc precursor solution described in S1 on the surface of the substrate to form a pattern through a printing device, and obtaining a patterned zinc oxide film through thermal curing and annealing; S3, transferring the patterned zinc oxide film described in S2 to the surface of a flexible substrate, and then making electrodes on the patterned zinc oxide film to obtain the patterned hydrovoltaic power generation device.

2. The method for preparing a patterned hydrovoltaic power generation device according to claim 1, characterized in that: In S1, the mass ratio of the complexing agent, the zinc salt and the reducing sugar is 1:(0.5-3):(0.1-2).

3. The method for preparing a patterned hydrovoltaic power generation device according to claim 1, characterized in that: In S1, the complexing agent is selected from polyethyleneimine or its derivatives; the zinc salt is selected from one or more of zinc nitrate, zinc acetate, zinc sulfate and zinc chloride; and the reducing sugar is selected from one or more of maltose, chitosan and glucose.

4. The method for preparing a patterned hydrovoltaic power generation device according to claim 1, characterized in that: In S1, the viscosity of the zinc precursor solution is 25 Pa s-70 Pa s.

5. The method for preparing a patterned hydrovoltaic power generation device according to claim 1, characterized in that: In S2, the parameters of the printing device are: air pressure is 3kg / cm 2 -6kg / cm 2 , speed is 1mm / s-5mm / s.

6. The method for preparing a patterned hydrovoltaic power generation device according to claim 1, characterized in that: In S2, the number of winding lines of the pattern is 7-13, the line width is 100 μm-350 μm, the line spacing is 115 μm-390 μm, and the line length is 5 mm-25 mm.

7. The method for preparing a patterned hydrovoltaic power generation device according to claim 1, characterized in that: In S2, the thermal curing temperature is 80°C-120°C, and the time is 1 min-3 min.

8. The method for preparing a patterned hydrovoltaic power generation device according to claim 1, characterized in that: In S2, the annealing temperature is 600°C-900°C, and the time is 2h-5h.

9. The method for preparing a patterned hydrovoltaic power generation device according to claim 1, characterized in that: The substrate is selected from a silicon substrate and / or a quartz substrate; the flexible substrate is selected from a PMMA substrate and / or PDMS.

10. A patterned hydrovoltaic power generation device prepared by the method according to any one of claims 1 to 9.

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