A method and device for collecting flowing water energy for power generation based on metal oxides

Abstract

The present invention belongs to the field of new energy technology, and specifically relates to a method and device for collecting flowing water energy based on metal oxide electrodes. The present invention utilizes the oxygen vacancy structure of metal oxides to adsorb a large number of charged particles in water, thereby generating an electric potential on the surface. As the water region undergoes continuous flow changes, the electric potential on the surface of the metal oxide electrode changes steadily. The reference electrode maintains its electric potential regardless of any flow in the water, acting as a reference potential, thereby continuously outputting electrical energy. The method specifically includes: electrochemically oxidizing a metal electrode to obtain a metal oxide electrode; placing multiple metal oxide electrodes and a reference electrode in a connected, flowing water region; and connecting an electric energy collection device to the metal oxide electrodes and reference electrodes with wires to measure the circuit voltage and current and collect the electrical energy. The method is simple and has high economic, environmental, and social benefits.

Description

Technical Field

[0001] The present invention belongs to the field of new energy technology, and in particular relates to a method and device for collecting flowing water energy for power generation based on metal oxide electrodes. Background Art

[0002] Hydropower is an important green energy. Compared with other traditional fossil energy sources, hydropower is pollution-free, reusable, has huge potential, and is also the focus of current development in the new energy field.

[0003] Currently, the most widely used method for harnessing hydropower is to use the impact of water flow to drive hydroelectric generators, converting the water's potential energy into mechanical energy, which is then converted into electrical energy. This traditional hydropower generation method suffers from drawbacks such as bulky equipment, high construction costs, terrain limitations, and the potential for ecological disruption caused by the construction of large reservoirs. More importantly, it cannot utilize weak water energy, severely limiting its efficient utilization and development. Therefore, more methods for harvesting hydropower are urgently needed.

[0004] Many researchers have developed nanohydrovoltaic generators based on the electrical potential generated by the coupling of nanomaterials like carbon and graphene with water. These generators are designed to directly harvest the kinetic energy of flowing water, the wave energy of seawater, and the evaporation energy of water vapor. However, key challenges currently exist, including the nanoscale limitations of these materials, the difficulty of fabrication, low power generation efficiency, limited total power generation, and the high ion concentration requirement in the water, making them impractical for large-scale power generation. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention utilizes the unique oxygen vacancy structure of metal oxides to adsorb a large number of charged particles in water, thereby generating an electric potential on its surface; when the water area continues to flow and change, the potential on the surface of the metal oxide electrode changes steadily, while the potential of the reference electrode does not change, thereby forming a potential difference and continuously outputting electrical energy.

[0006] To achieve the above objectives, an embodiment of the present invention provides a method for collecting flowing water energy for power generation based on metal oxide electrodes, the method specifically comprising the following steps:

[0007] Oxidizing a metal electrode using an electrochemical oxidation method to obtain a metal oxide electrode; the metal electrode is any one of tungsten, tantalum or molybdenum;

[0008] Placing multiple metal oxide electrodes and a reference electrode in a connected and flowing water region;

[0009] The electric energy collection device is connected to the metal oxide electrode and the reference electrode with wires to measure the loop voltage and current and collect electric energy.

[0010] Furthermore, the step of oxidizing the pure metal electrode by electrochemical oxidation to obtain the tungsten oxide electrode is specifically as follows:

[0011] Place the pure metal electrode in a sulfuric acid solution and electrochemically oxidize it 15-30 times using cyclic voltammetry;

[0012] The process parameters of the cyclic voltammetry are: scanning voltage of 1-2-1V, and scanning rate of 0.02-0.1V / s.

[0013] Furthermore, the reference electrode has a resistance of less than 10 4 Ω metal electrode or silicon carbide electrode.

[0014] Furthermore, the collection method further includes:

[0015] When the reference electrode is an Ag / AgCl electrode, a saturated calomel electrode or a SiC electrode, its resistance is greater than 10 4 When Ω is greater than Ω, an auxiliary electrode is set to measure the current flowing through the oxide electrode.

[0016] The metal oxide electrode leads out a wire to connect to the back-end circuit, and the connection between the metal oxide electrode and the wire needs to be sealed to prevent contact with water.

[0017] Based on the unified inventive concept, an embodiment of the present invention also provides a flowing water power generation and collection device based on metal oxide electrodes, wherein the flowing water power generation and collection device includes an oxide electrode and a reference electrode; the metal oxide electrode and the reference electrode are arranged in a connected and flowing water area; the metal oxide electrode and the reference electrode are connected to the electric energy collection device with a wire.

[0018] Furthermore, there may be a plurality of metal oxide electrodes, which are connected in series or in parallel.

[0019] Furthermore, when the reference electrode resistance is greater than 10 4 Ω, the flowing water power generation and collection device also includes an auxiliary electrode to measure the loop current.

[0020] Furthermore, when the ion concentrations of the connected and flowing water areas are different, the electric energy collected by the flowing water power generation and collection device is different. In water areas with low ion concentrations, the collected voltage is higher; in water areas with high ion concentrations, the collected voltage is lower.

[0021] Beneficial effects:

[0022] The present invention provides a new hydropower generation device. Compared with hydrovoltaic generators based on nanostructures such as carbon nanotubes and graphene, the hydrovoltaic power generation method and device can achieve stable power generation on a macro scale, and the power generation capacity is dozens of times that of nanogenerators. At the same time, the device has a simple structure and production and low cost.

[0023] The present invention provides a new method for generating electricity from flowing water, which can continuously obtain electricity from flowing water in a clean and pollution-free manner, has high economic, environmental and social benefits, and also has technical potential for practical application. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 A schematic structural diagram of a flowing water energy generation and collection device based on metal oxide electrodes provided in an embodiment of the present invention;

[0025] Figure 2 This is a demonstration diagram of the water power generation and collection of the electric quantity and water flow channel system provided in Example 1 of the present invention;

[0026] Figure 3 A graph showing the relationship between open circuit voltage and water flow velocity provided in Example 1 of the present invention;

[0027] Figure 4 A graph showing the relationship between open circuit voltage and water flow rate at different ion concentrations provided in Example 1 of the present invention;

[0028] Figure 5 A graph showing the relationship between the path current and the water flow velocity provided in Example 1 of the present invention;

[0029] Figure 6 A graph showing the relationship between open circuit voltage and water flow velocity provided in Example 2 of the present invention;

[0030] Figure 7 A graph showing the relationship between the path current and the water flow velocity provided in Example 2 of the present invention;

[0031] Figure 8 A graph showing the relationship between open circuit voltage and water flow velocity provided in Example 3 of the present invention;

[0032] Figure 9 This is a relationship diagram between the path current and the water flow velocity provided in Example 3 of the present invention.

[0033] The symbols in the accompanying drawings are specifically:

[0034] 1-1, metal oxide electrode; 1-2, reference electrode; 2-1, metal oxide electrode; 2-2, reference electrode; 2-3, auxiliary electrode; 2-4, liquid reservoir; 2-5, peristaltic pump; 2-6, connecting hose. DETAILED DESCRIPTION

[0035] To more clearly illustrate the technical content of the present invention, a detailed description is provided herein with reference to specific embodiments and accompanying drawings. Obviously, the examples listed are only preferred implementations of the present technical solution. Other technical solutions that can be readily derived by those skilled in the art based on the disclosed technical content still fall within the scope of protection of the present invention. In an embodiment of the present invention, a method for collecting flowing water energy for power generation based on metal oxide electrodes includes the following steps:

[0036] A metal electrode with a purity greater than 99.99% is electrochemically oxidized in a 0.1 mol / L H₂SO₄ solution using cyclic voltammetry for 15-30 cycles, with a sweep voltage of 1-2-1 V and a sweep rate of 0.02-0.1 V / s. Chemical oxidation can also be used for metal oxide electrodes. The prepared metal oxide electrode is connected to the back-end circuit via a wire. The connection between the electrode and the wire must be sealed to prevent contact with water.

[0037] The reference electrode should be a metal electrode with low resistivity. If the selected reference electrode has high resistance, an auxiliary electrode can be introduced to measure the current flowing through the oxide electrode. The tungsten oxide electrode and the reference electrode are placed in a connected and flowing water area. When the water flows through the oxide electrode, a double electric layer will form on the surface of the oxide electrode in contact with the water. The greater the water flow rate, the greater the streaming potential formed by the interaction between the oxide electrode and the water flow, and the more significant the flowing water energy effect.

[0038] When the internal resistance of the reference electrode is low, the tungsten oxide electrode and the reference electrode form both a voltage circuit and a current circuit. When the internal resistance of the reference electrode is high, the tungsten oxide electrode and the reference electrode form a voltage circuit, while the tungsten oxide electrode and the auxiliary electrode form a current circuit. The product of the current circuit and the voltage circuit is the power generation.

[0039] like Figure 1 As shown, an embodiment of the present invention provides a structural schematic diagram of a flowing water power generation and collection device based on metal oxide electrodes, which includes multiple parallel metal oxide electrodes 1-1, a reference electrode 1-2 and an energy collection device, wherein the metal oxide electrode 1-1 and the reference electrode 1-2 are arranged in a connected and flowing water area, and the solid metal oxide electrode 1-1 can adsorb a large number of charged particles in the water through the unique oxygen vacancy structure on the surface, thereby generating an electric potential on the surface; when the water area undergoes continuous flow changes, the electric potential on the surface of the metal oxide electrode will undergo stable changes; and the reference electrode 1-2 has an electric potential that remains unchanged in the water regardless of any flow, and acts as a reference potential, thereby continuously outputting electric energy.

[0040] Example 1

[0041] like Figure 2As shown, the embodiment of the present invention has built a quantitative water flow channel system to prove that the energy of flowing water can be continuously converted into electrical energy, which includes a liquid storage tank 2-4, a connecting hose 2-6, a peristaltic pump 2-5, a metal oxide electrode 2-1, a reference electrode 2-2 and an auxiliary electrode 2-3. In Example 1 of the present invention, a pure tungsten electrode with a purity greater than 99.99% is electrochemically oxidized 20 times in a 0.1 mol / L H2SO4 solution using cyclic voltammetry, with a scanning voltage of 1-2-1V and a scanning rate of 0.05 mV / s. After oxidation, its surface consists of a tight WO3 inner layer and a relaxed WO3.xH2O outer layer. The tungsten oxide electrode prepared by the electrochemical oxidation method is used as the metal oxide electrode 1-1, as shown Figure 1 shown.

[0042] In this embodiment 1, a tungsten oxide sheet with a thickness of 0.5 mm and an area of ​​5*10 mm is used, which has a large contact area with the water flow; multiple tungsten oxide electrodes 2-1 are installed in the flow pipe, and the electrical signal is drawn out with a wire clamp, and the middle is sealed and fixed with hot melt adhesive, such as Figure 2 shown.

[0043] Reference electrode 2-2 is a saturated Ag / AgCl electrode. Because the reference electrode has excessive resistance, a platinum electrode with low resistance is introduced as an auxiliary electrode for current detection. The present invention is not limited to the type of reference electrode; metal electrodes with stable potential in flowing liquids, silicon carbide electrodes, and the like, with low internal resistance, can be used.

[0044] An open circuit voltage E detection unit is provided between the tungsten oxide electrode 2-1 and the reference electrode 2-2, and a current I detection unit is provided between the tungsten oxide electrode and the auxiliary electrode. Both the open circuit voltage E detection unit and the current I detection unit are tested using an electrochemical workstation.

[0045] In Example 1 of the present invention, the peristaltic pump is controlled to make the water flow rate in the pipeline 0.0166, 0.0332, 0.0497, 0.0664, 0.0830, 0.0996, 0.1162, 0.01328, 0.1494, 0.1660, 0.1826 (m / s) respectively. The real-time flow rate response measured by the open circuit voltage detection unit E is as follows: Figure 3 As shown in the figure, it can be found that the tungsten oxide electrode responds instantaneously to the water flow velocity. At a water flow velocity of ~0.18m / s, a voltage of up to 40mV is generated. The flow velocity and voltage are linearly correlated, and the sensitivity is about 0.19200V / (m / s). In this embodiment, Figure 2 The water flow channel system of the quantitative peristaltic pump shown in the figure can provide a maximum water flow rate of 0.189m / s. Figure 3The response characteristics shown in the figure show that the tungsten oxide electrode can respond to higher flow rates and generate a larger stream potential. Tests were conducted on water flows with different ion concentrations: when the flow rate parameters in the water area were the same, they were 0.0332, 0.0664, 0.0996, 0.01328, and 0.1660 (m / s), respectively. The stream potential generated by the tungsten oxide electrode in water areas with different ion concentrations was different; Figure 4 As shown in the figure, the real-time flow rate responses of the tungsten oxide electrode in pure water, tap water, 0.01 mol / L KCl solution, and 0.1 mol / L KCl solution are similar, but the response sensitivities are different. In pure water with a low ion concentration, the streaming potential generated by the tungsten oxide electrode is close to 2 V, while in a 0.1 mol / L KCl solution with a high ion concentration, the streaming potential generated by the tungsten oxide electrode is close to 15 mV.

[0046] In Example 1, since a saturated Ag / AgCl electrode was used as the reference electrode, its internal resistance was close to 10 9 Ω, resulting in the current between the tungsten oxide electrode and the reference electrode circuit being too small to be easily collected. Therefore, an internal resistance of less than 10 4 The auxiliary electrode (platinum electrode) of Ω is used to test the current change caused by water flow. The flow rates are set to 0.0332, 0.0664, 0.0996, 0.01328, and 0.1660 (m / s). The real-time response measured by the current I detection unit is as follows: Figure 5 As shown: It can be found that the flow rate and current are also linearly related, with a sensitivity of 0.00022A / (m / s).

[0047] Example 2

[0048] In Example 2 of the present invention, a metal tantalum rod with a diameter of 3 mm and a length of 20 mm is used.

[0049] In Example 2, a tantalum oxide electrode is used as the working electrode 1-1, and a reference electrode 1-2 and an electric energy collection device are also included. Figure 1 As shown; the preparation method of the tantalum oxide electrode 1-1 is the same as the preparation method of the tungsten oxide electrode described above, and the prepared tantalum oxide electrode 1-1 is Figure 2 Tests were conducted in the quantitative water flow channel system shown to confirm that the tantalum oxide electrode 1-1 can continuously convert flowing water energy into electrical energy.

[0050] In Example 2, the peristaltic pump is controlled and the water flow velocity in the pipeline is set to be gradually superimposed, namely 0.0332, 0.0664, 0.0996, 0.01328, and 0.1660 (m / s). The real-time flow rate response measured by the open circuit voltage detection unit E is as follows: Figure 6As shown, the tantalum oxide electrode shows a transient response to water flow velocity. At a flow velocity of ~0.17 m / s, the generated voltage reaches as high as 150 mV. Furthermore, the relationship between flow velocity and voltage exhibits good linearity and additive properties, with a sensitivity of approximately 0.9987 V / (m / s).

[0051] Similarly, in Example 2, since the internal resistance of the reference electrode (saturated Ag / AgCl electrode) is close to 10 9 Ω, the internal resistance is too large, resulting in the current between the tantalum oxide electrode and the reference electrode circuit being too small to be easily collected. Therefore, the internal resistance is less than 10 4 The auxiliary electrode (platinum electrode) of Ω is used to test the current change caused by water flow. The flow rate is set to be gradually superimposed, respectively 0.0332, 0.0664, 0.0996, 0.01328, 0.1660 (m / s). The real-time response measured by the current I detection unit is as follows Figure 7 As shown in the figure, it can be found that the flow rate and current are also linearly related, with a sensitivity of 0.00043A / (m / s).

[0052] Example 3

[0053] In Example 3 of the present invention, a metal molybdenum rod with a diameter of 3 mm and a length of 20 mm is used.

[0054] Example 3 of the present invention uses a molybdenum oxide electrode as the working electrode 1-1, and also includes a reference electrode 1-2 and an electric energy collection device, such as Figure 1 As shown; the preparation method of the molybdenum oxide electrode 1-1 is consistent with the preparation method of the tungsten oxide and tantalum oxide electrodes described above, and the prepared molybdenum oxide electrode 1-1 is Figure 2 The test was carried out in the quantitative water flow channel system shown to confirm that the molybdenum oxide electrode 1-1 can continuously convert the flowing water energy into electrical energy.

[0055] In Example 3, the peristaltic pump is controlled and the water flow velocity in the pipeline is set to gradually decrease to 0.1660, 0.01328, 0.0996, 0.0664, and 0.0332 (m / s). The real-time flow rate response measured by the open circuit voltage detection unit E is as follows: Figure 8 As shown in the figure, the tantalum oxide electrode shows a transient response to water flow velocity. At a flow velocity of ~0.17 m / s, the generated voltage reaches as high as 150 mV. Furthermore, the relationship between flow velocity and voltage exhibits good linearity and additive properties, with a sensitivity of approximately 0.9887 V / (m / s).

[0056] Similarly, in Example 3, since the internal resistance of the reference electrode (saturated Ag / AgCl electrode) is close to 10 9 Ω, the internal resistance is too large, resulting in the current between the molybdenum oxide electrode and the reference electrode circuit being too small to be easily collected. Therefore, the internal resistance is less than 10 4The auxiliary electrode (platinum electrode) of Ω is used to test the current change caused by water flow. The flow rate is set to decrease gradually, respectively to 0.1660, 0.01328, 0.0996, 0.0664, 0.0332 (m / s). The real-time response measured by the current I detection unit is as follows Figure 9 As shown in the figure, it can be found that the flow rate and current are also linearly related, with a sensitivity of 0.00018A / (m / s).

[0057] In summary, it can be found that the hydrovoltaic power generation device based on metal oxide electrodes can continuously and stably output electrical energy in flowing water. The hydrovoltaic power generation device has a flexible design structure, simple production and low cost; and the power generation method is clean and pollution-free, and has high practical application potential.

[0058] The embodiments described above are only preferred specific implementation methods of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes based on the technical solutions and concepts of the present invention within the technical scope of the present invention, and they should be covered by the scope of protection of the present invention.

Claims

1. A method for collecting flowing water energy for power generation based on metal oxide electrodes, characterized in that: The power generation and collection method specifically comprises the following steps: Oxidizing a metal electrode by chemical oxidation or electrochemical oxidation to obtain a metal oxide electrode, wherein the metal electrode is any one of tungsten, tantalum, molybdenum, titanium, niobium or platinum; and the metal oxide surface has an oxygen vacancy structure; Placing multiple metal oxide electrodes and a reference electrode in a connected and flowing water region; Connecting the electric energy harvesting device to the metal oxide electrode and the reference electrode with wires, measuring the circuit voltage and current, and collecting electric energy; The method for collecting flowing water energy for power generation and collection is implemented based on a flowing water energy for power generation and collection device, which includes a metal oxide electrode and a reference electrode. The metal oxide electrode and the reference electrode are disposed in a connected and flowing water area. The metal oxide electrode and the reference electrode are connected to the power collection device with wires. The metal oxide electrodes are multiple and connected in series and parallel. The step of oxidizing the metal electrode to obtain the metal oxide electrode by electrochemical oxidation is specifically as follows: The metal electrode is placed in a sulfuric acid solution and electrochemically oxidized 15-30 times using cyclic voltammetry; The process parameters of the cyclic voltammetry are: scanning voltage of 1-2-1 V, scanning rate of 0.02-0.1 V / s; The reference electrode resistance is greater than 10 4 When Ω, set the auxiliary electrode; When the ion concentrations of the connected and flowing water areas are different, the electric energy collected by the flowing water power generation and collection device is different; in the water area with low ion concentration, the collected voltage is larger; in the water area with high ion concentration, the collected voltage is smaller.

2. The method for collecting flowing water energy based on metal oxide electrodes according to claim 1, characterized in that: The reference electrode has a resistance of less than 10 4 Ω metal electrode or silicon carbide electrode.

3. The method for collecting flowing water energy based on metal oxide electrodes according to claim 1, characterized in that: The collection method further comprises: When the reference electrode is an Ag / AgCl electrode, a saturated calomel electrode or a SiC electrode, its resistance is greater than 10 4 When Ω is equal to Ω, an auxiliary electrode is set to measure the current flowing through the tungsten oxide electrode.

4. A flowing water power generation and collection device based on the flowing water power generation and collection method according to any one of claims 1 to 3, characterized in that: The method for collecting flowing water energy for power generation is implemented based on a flowing water energy collection device, which includes a metal oxide electrode and a reference electrode. The metal oxide electrode and the reference electrode are arranged in a connected and flowing water area. The metal oxide electrode and the reference electrode are connected to the power collection device with wires. Placing multiple metal oxide electrodes and a reference electrode in a connected and flowing water region; Connecting the electric energy harvesting device to the metal oxide electrode and the reference electrode with wires, measuring the circuit voltage and current, and collecting electric energy; A metal electrode is oxidized by chemical oxidation or electrochemical oxidation to obtain a metal oxide electrode, wherein the metal electrode is any one of tungsten, tantalum, molybdenum, titanium, niobium or platinum; and the surface of the metal oxide has an oxygen vacancy structure.

5. The flowing water energy power generation and collection device according to claim 4, characterized in that: There are multiple metal oxide electrodes, which are connected in series and parallel with each other.

6. The flowing water energy power generation and collection device according to claim 4, characterized in that: When the reference electrode resistance is greater than 10 4 Ω, the flowing water power generation and collection device also includes an auxiliary electrode to measure the loop current.

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