A water photovoltaic power generation device and a preparation method and application thereof

Abstract

The application relates to the technical field of power generation materials, and discloses a water-driven power generation device and a preparation method and application thereof, wherein the water-driven power generation device is in a strip structure, the three-dimensional size of the water-driven power generation device is (0.001-3) cm*(0.001-3) cm*(0.2-20) cm, and the water-driven power generation device can be prepared by adopting a 3D printing method, a photocuring printing method, a silk screen printing method, an electrostatic spinning method, a casting method and the like. The prepared water-driven power generation device is small in size, high in water transmission efficiency and evaporation rate, and high in output density, one or more water-driven power generation devices can be connected in parallel or in series to amplify the performance, the electric performance of an integrated module is improved, and the water-driven power generation device is suitable for large-scale practical application.

Description

Technical Field

[0001] This invention belongs to the field of power generation materials technology, specifically relating to a water-based photovoltaic power generation device, its preparation method, and its application. Background Technology

[0002] With the growth of global energy demand, clean energy harvesting technologies with low or even net-zero carbon emissions are of great significance for achieving a sustainable supply of clean energy.

[0003] Hydroelectric generators (HEGs) are a type of hydroelectric generator that produces electricity by absorbing ambient heat and achieving ion transport and separation during effective evaporation. They are considered a potential power source due to their universality, self-sufficiency, and DC output, making them a highly promising continuous, zero-carbon emission power generation technology.

[0004] Existing hydrovolt generators use thin-film structure power generation devices, which have low water transport efficiency and evaporation rate. This is because the Poisson vane distribution of the thin film during the evaporation process is fast at both ends and slow in the middle. As the area of ​​the device increases, the water transport capacity in the middle area of ​​the device is prone to decrease, resulting in a decrease in power density. In addition, if thin-film structure power generation devices are to be used in practice, a large amount of water and water tanks are required, which is not suitable for large-scale practical applications. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a water-based photovoltaic power generation device, its preparation method and application. The prepared water-based photovoltaic power generation device has a three-dimensional strip structure, small size, high water transmission efficiency and evaporation rate, and high output density. The performance can be amplified by connecting one or more water-based photovoltaic power generation devices in parallel or in series, thereby improving the electrical performance of the integrated module and making it suitable for large-scale practical applications.

[0006] This invention provides the following technical solution:

[0007] In a first aspect, a water-based photovoltaic power generation device is provided, wherein the water-based photovoltaic power generation device has a strip-shaped structure and its three-dimensional dimensions are (0.001~3)cm*(0.001~3)cm*(0.2~20)cm.

[0008] Furthermore, the cross-sectional shape of the photovoltaic power generation device is one of the following: circular, elliptical, rectangular, triangular, or polygonal.

[0009] Furthermore, the material of the photovoltaic power generation device is one of reduced graphene oxide and multi-walled carbon nanotube composite material, or amorphous carbon.

[0010] In a second aspect, a method for preparing the hydroelectric power generation device described in the first aspect is provided, wherein the method is one of 3D printing, photopolymerization printing, screen printing, electrospinning, and casting.

[0011] Furthermore, the 3D printing method includes the following steps:

[0012] An aqueous solution of ascorbic acid was added to a suspension of graphene oxide, and after centrifugation, washing, filtration and concentration, reduced graphene oxide ink was obtained.

[0013] Concentrated sulfuric acid and concentrated nitric acid were added sequentially to multi-walled carbon nanotubes, and the mixture was stirred and reacted in an oil bath and condensation environment. After post-treatment, acidified multi-walled carbon nanotube ink was obtained.

[0014] Reduced graphene oxide ink and acidified multi-walled carbon nanotube ink are mixed, extruded using a 3D printer, and simultaneously freeze-dried in a suspended manner to obtain a composite hydrovoltaic device of reduced graphene oxide and multi-walled carbon nanotubes.

[0015] Furthermore, the concentration of the graphene oxide suspension is 3~15 mg·mL. -1 The concentration of the ascorbic acid aqueous solution is 20~100 mg·mL. -1 The volume ratio of the ascorbic acid aqueous solution to the graphene oxide suspension is 1:(9~11). If the concentrations of the ascorbic acid aqueous solution and the graphene suspension are low, the reduction time is long, or it may not be possible to reduce it to a centrifugable state, thus preventing the graphene oxide suspension from becoming partially reduced graphene oxide ink. If the concentration is too high, over-reduction may occur, leading to water loss in the slurry and making it impossible to prepare reduced graphene oxide ink.

[0016] Furthermore, the concentrated sulfuric acid has a mass concentration of 98%, the concentrated nitric acid has a mass concentration of 98%, the mass ratio of the multi-walled carbon nanotube to the sum of the volumes of the concentrated sulfuric acid and concentrated nitric acid is 1 g:(40~50) mL, and the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1.

[0017] Furthermore, concentrated sulfuric acid and concentrated nitric acid were added sequentially to the multi-walled carbon nanotubes, and the reaction was stirred in an oil bath and condensation environment at 88~92℃ for 1.5~2.5h.

[0018] Furthermore, the post-processing includes: cooling the solution to room temperature, diluting it with deionized water, and performing vacuum filtration.

[0019] Furthermore, the reduced graphene oxide ink and the acidified multi-walled carbon nanotube ink are mixed at a mass ratio of 1:(0.1~4.0).

[0020] Furthermore, a direct-write 3D printer was used for extrusion at a temperature of 22–28°C, a pressure of 180–300 kPa, and a nozzle diameter of 210–1200 μm. Simultaneously, the extruder underwent suspended cryogenic shaping in a liquid nitrogen cryogenic shaping tank, followed by freeze-drying. Under these conditions, the resulting hydrovoltaic power generation device exhibited a dimensionally controllable strip structure and good power generation performance.

[0021] Furthermore, the photopolymerization printing method includes the following steps:

[0022] A precursor solution was prepared by mixing polyethylene glycol diacrylate (PEGDA), water, lithium phenyl-2,4,6-trimethylbenzoylphosphine (LAP), and pigment.

[0023] Using a photopolymer printer, the precursor solution is photopolymerized and printed according to a preset fiber model to obtain long strip fibers;

[0024] Long, straight fibers are freeze-dried and then calcined to obtain amorphous carbon-water photovoltaic devices.

[0025] Furthermore, in the precursor solution, the mass ratio of polyethylene glycol diacrylate, water, lithium phenyl-2,4,6-trimethylbenzoylphosphinic acid and pigment is (20~10):(80~90):(0.3~0.6):0.1.

[0026] Furthermore, during the photopolymerization printing process, the following parameters are set: layer thickness is 0.001~1 mm, bottom layer thickness is 0.001~10 mm, number of bottom layers is 1~10, exposure time is 1~5 s, and bottom layer exposure time is 10~60 s.

[0027] Furthermore, the freeze-drying method includes: placing long strips of fiber in a straight line in a petri dish, then placing the petri dish in a liquid nitrogen tank to freeze, and immediately placing it in a freeze dryer for freeze-drying.

[0028] Furthermore, the calcination method includes: placing the freeze-dried fibers in a straight line in a quartz boat, annealing them at 480~550℃ for 100~500 min under a nitrogen atmosphere, and then removing them after they have naturally cooled to room temperature.

[0029] Thirdly, the application of the photovoltaic power generation device described in the first aspect or the photovoltaic power generation device prepared by the method described in the second aspect in the field of photovoltaic power generation is provided.

[0030] Compared with the prior art, the beneficial effects of the present invention are:

[0031] (1) This invention proposes for the first time a three-dimensional strip-shaped water-based photovoltaic power generation device. The three-dimensional dimensions of the water-based photovoltaic power generation device can be reduced to (0.001~3)cm*(0.001~3)cm*(0.2~20)cm. Compared with the thin film structure in the prior art, the significant reduction in three-dimensional dimensions increases the water flow rate, enhances the water transmission capacity, and increases the output power density, enabling a power density of 14W·m. -2 Its high output power density surpasses that of any device reported in any current technology;

[0032] (2) The water-based photovoltaic power generation device proposed in this invention is small in size and has low volume requirements for water source. The performance can be amplified by connecting one or more water-based photovoltaic power generation devices in parallel or in series. The prepared water-based photovoltaic power generation device can achieve power output from 0.01 microwatts to 500 watts, improve the electrical performance of the integrated module, significantly simplify the integrated module, reduce the amount and volume of water tank used, and is suitable for large-scale practical applications.

[0033] (3) The water-voltaic power generation device provided by the present invention can be prepared by one of 3D printing, photopolymerization printing, screen printing, electrospinning, and casting. In this process, the reduced graphene oxide ink and the acidified multi-walled carbon nanotube ink are mixed and extruded by a 3D printer. At the same time, the suspended freeze-drying is carried out. The freeze-shaping is performed at the same time as printing, and the printing can be completed without a substrate. This solves the problem of structural damage caused by uneven stress on the part in contact with the substrate during the freeze-shaping process when printing fiber structures in the prior art due to the presence of a substrate. It also broadens the diversity of printed structures. Attached Figure Description

[0034] Figure 1 This is a dotted line graph showing the changes in voltage and current density of the rGO / CNTs microrod as the external load resistance changes in Embodiment 1 of the present invention.

[0035] Figure 2 This is a line graph showing the change in output power density of the rGO / CNTs microrods as a function of external factors in Embodiment 1 of the present invention. Detailed Implementation

[0036] The present invention will be further described below with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and should not be used to limit the scope of protection of the present invention.

[0037] Example 1

[0038] This embodiment uses 3D printing to fabricate a hydroelectric power generation device, and the steps are as follows:

[0039] (1) Add 100 mL of solution with a concentration of 10 mg·mL -110 mL of a 100 mg·mL⁻¹ graphene oxide (GO) suspension was added. -1 The ascorbic acid (L-AA) aqueous solution was centrifuged, washed, filtered and concentrated to obtain reduced graphene oxide (rGO) ink.

[0040] (2) Weigh 1.0 g of multi-walled carbon nanotubes (CNTs) and add them to a three-necked flask. Then add 33 mL of concentrated H2SO4 with a mass concentration of 98% and 11 mL of concentrated HNO3 with a mass concentration of 98% in sequence. Stir vigorously for 2 h in an oil bath and condensation environment at 90℃. Cool the solution to room temperature, dilute it with a large amount of deionized water, and vacuum filter it to obtain acidified CNTs ink.

[0041] (3) The rGO ink and acidified CNTs ink were mixed at a mass ratio of 1:2 using a homogenizer and then extruded using a direct-write 3D printer. The extrusion temperature was room temperature, the nozzle pressure was 180 kPa, and the nozzle diameter was 550 μm. While the 3D printer was extruding, it was suspended and cryogenically shaped in a liquid nitrogen cryogenic shaping tank, and then freeze-dried in a freeze dryer to obtain reduced graphene oxide and multi-walled carbon nanotube composite (rGO / CNTs) microrods (with a circular cross-section).

[0042] (4) Cut the rGO / CNTs microrods prepared in step (3) into heights of 0.3 cm, 0.5 cm, 1.0 cm, 1.5 cm and 2.0 cm for later use.

[0043] Example 2

[0044] This embodiment uses 3D printing to fabricate a hydroelectric power generation device, and the steps are as follows:

[0045] (1) Add 100 mL of solution with a concentration of 10 mg·mL -1 Add 10 mL of GO suspension with a concentration of 100 mg·mL⁻¹ -1 The L-AA aqueous solution was centrifuged, washed, filtered, and concentrated to obtain rGO ink.

[0046] (2) Weigh 1.0g of CNTs and add them to a three-necked flask. Then add 33 mL of concentrated H2SO4 with a mass concentration of 98% and 11 mL of concentrated HNO3 with a mass concentration of 98% in sequence. Stir vigorously for 2 hours in an oil bath and condensation environment at 90℃. Cool the solution to room temperature, dilute it with a large amount of deionized water, and filter it under vacuum to obtain acidified CNTs ink.

[0047] (3) The rGO ink and acidified CNTs ink were mixed at a mass ratio of 1:2 using a homogenizer and then extruded using a direct-write 3D printer. The extrusion temperature was room temperature and the nozzle pressure was 180 kPa. The nozzle diameters were 260 µm, 410 µm, 550 µm, 840 µm and 1200 µm respectively. While the 3D printer was extruding, the ink was suspended and cryogenically shaped in a liquid nitrogen cryogenic shaping tank. Then it was freeze-dried in a freeze dryer and cut into rGO / CNTs microrods with different diameters and a height of 0.5 cm.

[0048] Example 3

[0049] This embodiment uses 3D printing to prepare hydrovoltaic power generation devices. The difference from embodiment 2 is that: in step (3), rGO ink and acidified CNTs ink are mixed in a mass ratio of 1:2 using a homogenizer, and then extruded using a direct-write 3D printer. The extrusion temperature is room temperature, the nozzle pressure is 180 kPa, and different shaped nozzles are used. While the 3D printer is extruding, it is suspended in a liquid nitrogen cryogenic shaping tank for cryogenic shaping, and then freeze-dried by a freeze dryer. The rGO / CNTs with a height of 10 cm are cut, and the cross-sectional shapes are circular, elliptical, rectangular, triangular, and pentagonal, respectively.

[0050] Example 4

[0051] This embodiment uses 3D printing to prepare a water-voltaic power generation device. The difference from embodiment 1 is that: in step (3), rGO ink and acidified CNTs ink are mixed at mass ratios of 1:0, 1:0.1, 1:1, 1:2, 1:3, and 1:4, respectively, and the corresponding mass percentages of CNTs in the ink mixture are 0%, 0.1%, 1%, 2%, 3%, and 4%, respectively; in step (4), rGO / CNTs microrods are cut to a height of 0.5 cm.

[0052] Example 5

[0053] Using the rGO / CNTs microrods prepared in Example 1, a hydrovoltaic power generation module was fabricated by screen printing. This example designed seven types of hydrovoltaic power generation modules: one microrod device, ten microrod devices connected in parallel and series, one hundred microrod devices connected in parallel and series, and one hundred and fifty microrod devices connected in parallel and series. The largest sample, with 1050 microrod devices connected in parallel, is approximately the size of an adult's palm. This planar design significantly reduces the integration area. Compared to traditional thin-film device integration, which requires a large amount of solid water, the microrod structure of the hydrovoltaic power generation module is smaller in size, reducing dependence on water sources. Furthermore, the above-mentioned hydrovoltaic power generation modules can be used to fabricate hydrovoltaic power generation devices, achieving power output from 0.01 microwatts to 500 watts.

[0054] Example 6

[0055] This embodiment uses photopolymerization printing to fabricate a water-based photovoltaic device. The specific steps are as follows:

[0056] (1) Mix PEGDA, water, LAP and lemon yellow in a mass ratio of 10:80:0.6:0.1 to obtain a precursor solution.

[0057] (2) Using a photopolymer printer, set the parameters as follows: layer thickness is 0.01 mm, bottom layer thickness is 0.01 mm, number of bottom layers is 3, exposure time is 2 s, bottom layer exposure time is 50 s, and the precursor solution is photopolymerized and printed according to the preset fiber model to obtain long strip fibers.

[0058] (3) Place the long fibers in a straight line in a petri dish, then put the petri dish into a liquid nitrogen tank to freeze, and immediately put it into a freeze dryer to freeze dry.

[0059] (4) The freeze-dried fibers were placed in a quartz boat in a straight line. Under a nitrogen atmosphere, the temperature was raised from 30°C to 500°C in 235 min. The temperature was kept at 500°C for 120 min. After naturally cooling to room temperature, the fibers were removed to obtain amorphous carbon strip-shaped hydrovoltaic devices with cross-sectional shapes of circles, ellipses, rectangles, triangles and pentagons and a height of 10 cm.

[0060] Comparative Example 1

[0061] Acidified multi-walled carbon nanotube powder was dispersed in deionized water to form an electrode solution with a concentration of 10 mg / mL. Then, the electrode solution was coated on both ends of a reduced graphene oxide film using a brush to form upper and lower electrodes. Wires were added to the electrodes and led out, thus preparing a thin-film structured water-voltaic power generation device with a length and width of 0.5 cm.

[0062] Performance Comparison

[0063] (1) Electrical performance tests were conducted on the rGO / CNTs microrod devices with the same diameter (550μm) but different heights in Example 1. The voltage and current were tested, and the results are shown in Table 1 below.

[0064] Table 1. Electrical performance test results of devices with a diameter of 550 μm and different heights.

[0065]

[0066] As shown in Table 1, as the height of the microrod device increases from 0.3 cm to 0.5 cm, its voltage gradually increases to 1.1 V. After that, as the height increases, the voltage tends to stabilize, while the current shows a trend of first increasing and then decreasing, reaching its maximum value when the height is 0.5 cm.

[0067] (2) Electrical performance tests were conducted on the rGO / CNTs microrod devices with the same height (0.5 cm) but different diameters in Example 2. The voltage and current were tested, and the results are shown in Table 2 below.

[0068] Table 2. Electrical performance test results of devices with a height of 0.5 cm and different diameters.

[0069]

[0070] As shown in Table 2, as the diameter of the microrod device increases, the voltage remains almost constant, while the current increases with the increase in diameter.

[0071] (3) The output power density of the rGO / CNTs microrod device with a diameter of 550 µm and a height of 0.5 cm in Example 1 was tested by external load resistance. The changes in voltage and current density were tested by changing the connection method. Figure 1 and Figure 2 It can be seen that a microrod device with a diameter of 550 µm and a height of 0.5 cm can achieve 14.3 W / m². -2 Its output power density is the best reported in current hydroelectric power generation operations.

[0072] (4) The output power density of rGO / CNTs with different cross-sectional shapes prepared by the 3D printing method in Example 3 was tested by external load resistance. The results are shown in Table 3 below.

[0073] Table 3 Output power density results of rGO / CNTs with different cross-sectional shapes using 3D printing method

[0074]

[0075] As shown in Table 3, the output power density performance gradually increases as the cross-sectional area decreases, regardless of the cross-sectional shape.

[0076] (5) The zeta potential and voltage of the rGO / CNTs microrods prepared in Example 4 were tested, and the results are shown in Table 4.

[0077] Table 4. Voltage performance variations of microrod devices fabricated with different CNT ratios.

[0078]

[0079] Table 4 shows that rGO / CNT microrods with different CNT ratios maintain good electrical properties. Specifically, as the CNT content increases from 0 to 2 wt%, the zeta potential gradually increases, indicating an increase in surface charge after the CNT conductive network is integrated. When the CNT content is further increased, the zeta potential remains almost unchanged because the rGO sheet is completely covered by CNTs. According to the classical electric double-layer theory, the zeta potential reflects the electric field of the rGO / CNT microrods; a higher zeta potential indicates more surface charge. Therefore, the output voltage increases with increasing CNT content. When the CNT content further increases, the voltage decreases slightly, possibly because the increased hydrophilicity of CNTs affects their evaporation rate and thus degrades performance.

[0080] (6) Voltage and current performance tests were conducted on the hydrovoltaic power generation modules prepared by parallel and series connection of 1, 10, 100 and 1050 devices in Example 5. The results are shown in Table 5.

[0081] Table 5. Electrical performance test results of hydroelectric power generation modules fabricated with different numbers of devices in parallel and series connection.

[0082]

[0083] As shown in Table 5, the voltage of 10 microrod devices connected in series is 11V, the voltage of 100 microrod devices connected in series is 108V, and the voltage of 1050 microrod devices connected in series is 1067V. The currents of the hydro-voltaic power generation modules with 10, 100, and 1050 microrod devices connected in parallel are 110µA, 1185µA, and 12840µA, respectively. The current increases approximately linearly with the increase in the number of microrod devices. When 1050 microrod devices are connected in parallel, the output power is 0.01W. This shows that the hydro-voltaic power generation device in this invention can achieve performance amplification through parallel and series connections, which is more beneficial for practical applications.

[0084] (7) The output power density of rGO / CNTs with different cross-sectional shapes prepared by the photopolymerization printing method in Example 6 was tested by external load resistance. The results are shown in Table 6 below.

[0085] Table 6 Output power density results of rGO / CNTs with different cross-sectional shapes using photopolymerization printing method

[0086]

[0087] As shown in Table 6, with different cross-sectional shapes, the output power density performance gradually increases as the cross-sectional area decreases. Furthermore, compared with Table 3, under the same conditions, the performance of the hydrovoltaic device prepared by 3D printing is superior to that prepared by photopolymerization printing.

[0088] (8) Flow rate tests were conducted on the microrod structure of Example 1 and the thin film structure of the water photovoltaic device of Comparative Example 1. Water was dripped at one end of the device, and the height of the water rising on the device over time was observed. The results are shown in Tables 7 and 8 below.

[0089] Table 7. Water rise height on the microrod structure device in Example 1

[0090]

[0091] Table 8. Water rise height on the thin-film structure device in Comparative Example 1

[0092]

[0093] As shown in Tables 7 and 8, within the same time period, compared with the thin film structure device of Comparative Example 1, the water rises to a greater height in the microrod structure device of Example 1, i.e., the flow rate is higher, indicating that the reduction of the three-dimensional size of the device will increase the flow rate.

[0094] (9) The evaporation rate of the microrod structure with a height of 0.5 cm in Example 1 and the thin film structure of the water photovoltaic power generation device in Comparative Example 1 were tested, and the results are shown in Table 9 below.

[0095] Table 9 Evaporation rates of the microrod structure in Example 1 and the thin film structure in Comparative Example 1

[0096]

[0097] As shown in Table 9, the reduction in device size leads to an increase in evaporation rate, which is more conducive to achieving high-performance hydroelectric power generation.

[0098] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A hydroelectric power generation device, characterized in that, The water-based photovoltaic power generation device has a strip-shaped structure with three-dimensional dimensions of (0.001~3)cm*(0.001~3)cm*(0.2~20)cm; The cross-sectional shape of the water-voltaic power generation device is one of the following: circular, elliptical, rectangular, triangular, or polygonal. The material of the hydrovoltaic power generation device is one of the following: reduced graphene oxide and multi-walled carbon nanotube composite material, or amorphous carbon. The method for preparing the hydrovoltaic power generation device is either 3D printing or photopolymerization printing. The 3D printing method includes the following steps: adding ascorbic acid aqueous solution to a graphene oxide suspension, followed by centrifugation, washing, filtration and concentration to obtain reduced graphene oxide ink; adding concentrated sulfuric acid and concentrated nitric acid sequentially to multi-walled carbon nanotubes, stirring and reacting in an oil bath and condensation environment, and then post-processing to obtain acidified multi-walled carbon nanotube ink; mixing the reduced graphene oxide ink and the acidified multi-walled carbon nanotube ink, extruding them using a 3D printer, and simultaneously performing suspended freeze-drying to obtain a composite hydrovoltaic device of reduced graphene oxide and multi-walled carbon nanotubes. The photopolymerization printing method includes the following steps: mixing polyethylene glycol diacrylate, water, lithium phenyl-2,4,6-trimethylbenzoylphosphinic acid and pigment to obtain a precursor solution; using a photopolymerization printer, photopolymerizing the precursor solution according to a preset fiber model to obtain long strip fibers; maintaining the long strip fibers in a straight state for freeze drying, and then calcining to obtain an amorphous carbon-water photovoltaic power generation device.

2. A method for preparing the water-based photovoltaic power generation device according to claim 1, characterized in that, The method is one of 3D printing and photopolymerization printing; The 3D printing method includes the following steps: An aqueous solution of ascorbic acid was added to a suspension of graphene oxide, and after centrifugation, washing, filtration and concentration, reduced graphene oxide ink was obtained. Concentrated sulfuric acid and concentrated nitric acid were added sequentially to multi-walled carbon nanotubes, and the mixture was stirred and reacted in an oil bath and condensation environment. After post-treatment, acidified multi-walled carbon nanotube ink was obtained. Reduced graphene oxide ink and acidified multi-walled carbon nanotube ink are mixed, extruded using a 3D printer, and simultaneously freeze-dried in a suspended manner to obtain a composite hydrovoltaic device of reduced graphene oxide and multi-walled carbon nanotubes.

3. The method for preparing a water-based photovoltaic power generation device according to claim 2, characterized in that, The concentration of the graphene oxide suspension is 3~15 mg·mL. -1 The concentration of the ascorbic acid aqueous solution is 20~100 mg·mL. -1 The volume ratio of the ascorbic acid aqueous solution to the graphene oxide suspension is 1:(9~11).

4. The method for preparing a water-based photovoltaic power generation device according to claim 2, characterized in that, The concentrated sulfuric acid has a mass concentration of 98%, the concentrated nitric acid has a mass concentration of 98%, the mass ratio of the multi-walled carbon nanotube to the sum of the volumes of the concentrated sulfuric acid and concentrated nitric acid is 1 g:(40~50) mL, and the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:

1.

5. The method for preparing a water-based photovoltaic power generation device according to claim 2, characterized in that, After adding concentrated sulfuric acid and concentrated nitric acid sequentially to multi-walled carbon nanotubes, the mixture was stirred and reacted in an oil bath and condensation environment at 88-92℃ for 1.5-2.5 hours.

6. The method for preparing a hydroelectric power generation device according to claim 2, characterized in that, The post-processing includes: cooling the solution to room temperature, diluting it with deionized water, and performing vacuum filtration.

7. The method for preparing a water-based photovoltaic power generation device according to claim 2, characterized in that, The reduced graphene oxide ink and the acidified multi-walled carbon nanotube ink are mixed at a mass ratio of 1:(0.1~4.0); The extrusion is performed using a direct-write 3D printer at an extrusion temperature of 22-28℃, a pressure of 180-300 kPa, and a nozzle diameter of 210-1200 μm. Simultaneously, the 3D printer performs suspended cryogenic shaping in a liquid nitrogen cryogenic shaping tank, followed by freeze drying in a freeze dryer.

8. The method for preparing a water-based photovoltaic power generation device according to claim 2, characterized in that, The photopolymerization printing method includes the following steps: A precursor solution was obtained by mixing polyethylene glycol diacrylate, water, lithium phenyl-2,4,6-trimethylbenzoylphosphinic acid, and pigment. Using a photopolymer printer, the precursor solution is photopolymerized and printed according to a preset fiber model to obtain long strip fibers; Long, straight fibers are freeze-dried and then calcined to obtain amorphous carbon-water photovoltaic devices.

9. The method for preparing a water-based photovoltaic power generation device according to claim 8, characterized in that, In the precursor solution, the mass ratio of polyethylene glycol diacrylate, water, lithium phenyl-2,4,6-trimethylbenzoylphosphinic acid and pigment is (20~10):(80~90):(0.3~0.6):0.1; And / or, during the photopolymerization printing, the following parameters are set: layer thickness is 0.001~1mm, bottom layer thickness is 0.001~10mm, number of bottom layers is 1~10, exposure time is 1~5s, and bottom layer exposure time is 10~60s; And / or, the freeze-drying method includes: placing long strips of fiber in a straight line in a petri dish, then placing the petri dish in a liquid nitrogen tank to freeze, and immediately placing it in a freeze dryer for freeze-drying after freezing; And / or, the calcination method includes: placing the freeze-dried fibers in a straight line in a quartz boat, annealing them at 480~550℃ for 100~500 min under a nitrogen atmosphere, and removing them after natural cooling to room temperature.

10. The application of the water-based photovoltaic power generation device according to claim 1 or the water-based photovoltaic power generation device prepared by the method according to any one of claims 2 to 9 in the field of water-based photovoltaic power generation.

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