Oscillating redox power plant, power generator and power generation method

Abstract

The application relates to the new energy technology field, in particular to an oscillation redox power generation device, a power generation device and a power generation method, which comprise: a first electrolyte and a second electrolyte; a diaphragm arranged between the first electrolyte and the second electrolyte; a first electrode arranged in the first electrolyte, a second electrode arranged in the second electrolyte and an external circuit arranged between the first electrode and the second electrode; when the external circuit is turned on, the first electrode is connected with the second electrode, a fifth electric potential is greater than a sixth electric potential, a first redox couple occurs reduction reaction and a second redox couple occurs oxidation reaction; when the external circuit is turned off, the first electric potential is restored to be greater than a third electric potential, the first redox couple occurs oxidation reaction, the second electric potential is restored to be less than a fourth electric potential, and the second redox couple occurs reduction reaction. Therefore, the specificity of an operation environment in the related art is solved, and the flexibility and wide application of the technology are limited.

Description

Technical Field

[0001] The present application relates to the field of new energy technology, and in particular to an oscillating redox power generation device, a power generation component, and a power generation method. Background Art

[0002] Energy is the cornerstone of social progress, and its importance is irreplaceable. With the widespread use of fossil fuels leading to increasingly severe energy depletion and global warming, human society stands at a critical juncture in energy transition. Against this backdrop, exploring and developing sustainable green energy has become a crucial mission of our times.

[0003] In recent years, the scientific community has made significant progress in the field of green energy, with the emergence of a series of cutting-edge power generation technologies, such as piezoelectricity, triboelectricity, thermoelectricity, moisture vapor, hydrovoltaicity, and osmotic energy. These technologies, based on unique physical effects or natural phenomena, achieve the goal of directly capturing energy from the environment and converting it into electricity, demonstrating enormous environmental potential and application prospects. However, these emerging technologies are often limited by specific operating environments, such as light, temperature, humidity, or salinity, which to some extent restricts their flexibility and widespread application. Summary of the Invention

[0004] The present application provides an oscillating redox power generation device, a power generation device and a power generation method to solve the problems in related technologies such as the high specificity of the operating environment, which limits the flexibility and wide application of the technology.

[0005] The first aspect of the present application provides an oscillating redox power generation device, comprising: a first electrolyte and a second electrolyte; a diaphragm arranged between the first electrolyte and the second electrolyte; a first electrode arranged in the first electrolyte, a second electrode arranged in the second electrolyte, and an external circuit arranged between the first electrode and the second electrode, the external circuit comprising a switch, wherein the first electrolyte comprises a first solvent and a first redox pair, the second electrolyte comprises a second solvent and a second redox pair, a first potential of the first electrode immersed in the first solvent is different from a second potential of the second electrode immersed in the second solvent, the redox potential of the first redox pair is different from a third potential and a fourth potential of the second redox pair, and the second potential of the first electrode immersed in the first electrolyte is determined according to the first potential and the third potential. A fifth potential is determined, based on the second potential and the fourth potential, to be a sixth potential of the second electrode immersed in the second electrolyte; when the external circuit is turned on, the first electrode is connected to the second electrode, and when the external circuit switch is closed, since the fifth potential is greater than the sixth potential, the first redox couple undergoes a reduction reaction, and the second redox couple undergoes an oxidation reaction, and based on the redox reaction of the asymmetric redox couple, the first potential and the second potential are asymmetric for coordinated discharge; when the external circuit switch is disconnected, if the first potential is restored to a level where the first potential is greater than the third potential, the first redox couple undergoes an oxidation reaction, and if the second potential is restored to a level where the second potential is less than the fourth potential, the second redox couple undergoes a reduction reaction, and based on the self-recovery of the first potential and the second potential, the first redox couple and the second redox couple are induced to recover to the state before the switch is closed.

[0006] Optionally, the first electrode, the second electrode, the first redox couple, and the second redox couple are hardly consumed.

[0007] Optionally, the first solvent and the second solvent respectively include at least one of water, salt solution, acid solution, alkaline solution, ionic liquid, and organic solvent.

[0008] Optionally, the first redox couple and the second redox couple respectively include at least one of a metal compound, a halide, and an aromatic compound.

[0009] Optionally, the material of the first electrode is the same as or different from the material of the second electrode, wherein, if the material of the first electrode is the same as the material of the second electrode, the first solvent is different from the second solvent; if the material of the first electrode is different from the material of the second electrode, the first solvent is the same as or different from the second solvent.

[0010] Optionally, the first electrode further includes a first current collector, the second electrode further includes a second current collector, the material of the first electrode is located on at least one side of the first current collector, the material of the second electrode is located on at least one side of the second current collector, and the first current collector and the second current collector are in the first electrolyte and the second electrolyte, respectively.

[0011] Optionally, the material of the first electrode and the material of the second electrode respectively include at least one of a metal element, a metal oxide, a hydroxide, a carbide, a sulfide, a nitride, a conductive polymer, and a carbon-based material.

[0012] Optionally, the first current collector and the second current collector respectively include at least one of graphite foil, aluminum foil, copper foil, and carbon cloth.

[0013] A second aspect of the present application provides a power generation device, comprising the above oscillating redox power generation device, wherein a plurality of power generation devices are connected in series and / or in parallel.

[0014] In a third aspect, an embodiment of the present application provides an oscillating redox power generation method, which utilizes the above oscillating redox power generation device to generate electricity, wherein the method includes the following steps: controlling the external circuit of the oscillating redox power generation device to be turned on, the first electrode is connected to the second electrode, and when the external circuit switch is closed, since the fifth potential is greater than the sixth potential, the first redox couple undergoes a reduction reaction, and the second redox couple undergoes an oxidation reaction, and the redox reaction of the asymmetric redox couple, the first potential, and the second potential are asymmetric and coordinated discharge is performed; after the external circuit switch of the oscillating redox power generation device is controlled to be turned off, the first potential and the second potential are respectively restored to the state before the external circuit is turned on; after the first potential and the second potential are restored, if the first potential is restored to the first potential being greater than the third potential, the first redox couple in the first electrolyte is induced to undergo an oxidation reaction, and if the second potential is restored to the second potential being less than the fourth potential, the second redox couple in the second electrolyte is induced to undergo a reduction reaction, and based on the self-recovery of the first potential and the second potential, the first redox couple and the second redox couple are induced to recover to the state before the switch is closed.

[0015] Therefore, this application has the following beneficial effects:

[0016] The embodiments of the present application construct an asymmetric interface structure by regulating the surface properties of the electrode material and the type of electrolyte to achieve the generation of a potential difference between the electrodes, such as the potential difference between the first potential and the second potential. The electrode charge state induced by solid-liquid contact has good self-recovery, and the electrode potential can still be restored to the state before discharge after discharge, and the two electrodes are almost not consumed during the power generation process. Therefore, when there is a redox couple in the electrolyte, and the redox potential of the redox couple and the electrode potential conform to a specific potential distribution, during the process of short-circuiting and disconnecting the external circuit switch, the redox couple will undergo a corresponding oxidation / reduction reaction or reduction / oxidation reaction, so that the first and second redox couples are not consumed during the power generation process; this oscillating redox reaction of the redox couple will cooperate with the power generation behavior of the potential difference between the first potential and the second potential itself to achieve enhanced power output. For example, the addition of a redox couple can slow down the rate of change of the electrode potential when the switch is closed, resulting in a higher voltage across the load under the same load; it can also speed up the recovery of the electrode potential after the switch is disconnected, allowing the device to operate at a faster switching frequency. The entire power generation process does not require pre-charging operations with an external power supply, enabling long-term cyclic power generation. The device does not rely on specific environmental conditions and allows for flexible selection of electrolytes, making it suitable for a variety of application scenarios, ranging from daily life to industrial production. This solves technical problems such as the high specificity of the operating environment in related technologies, which limits the flexibility and wide application of the technology.

[0017] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become apparent from the description below, or will be learned through practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the following description of the embodiments in conjunction with the accompanying drawings, in which:

[0019] Figure 1 This is an example diagram of an oscillating redox power generation device provided according to an embodiment of the present application;

[0020] Figure 2 This is an exemplary diagram of an oscillating redox power generation device provided according to one embodiment of the present application;

[0021] Figure 3 A schematic diagram of the solid surface zeta potential of a MnO2 electrode and a MoS2 electrode provided according to one embodiment of the present application;

[0022] Figure 4 Schematic diagram of the electrode potential of an MnO2 electrode in a first solvent and the electrode potential of a MoS2 electrode in a second solvent according to one embodiment of the present application;

[0023] Figure 5 Schematic diagram of the electrode potential of a MnO2 electrode in a first solvent and the electrode potential of a MoS2 electrode in a second solvent according to one embodiment of the present application;

[0024] Figure 6 Schematic diagram of the redox potential of I2 / KI and K3[Fe(CN)6] / K4[Fe(CN)6] according to one embodiment of the present application;

[0025] Figure 7 A schematic diagram of potential distribution provided according to an embodiment of the present application;

[0026] Figure 8 A schematic diagram of the electrical output performance of a device provided according to one embodiment of the present application;

[0027] Figure 9 A schematic diagram of a power density curve of a device provided according to one embodiment of the present application;

[0028] Figure 10 A schematic structural diagram of a device provided according to one embodiment of the present application;

[0029] Figure 11 A schematic diagram illustrating the integrated performance of a device provided according to one embodiment of the present application;

[0030] Figure 12 Schematic diagram of electrical output performance at different MoS2 electrode thicknesses according to one embodiment of the present application;

[0031] Figure 13 A schematic diagram of electrical output performance at different KCl concentrations provided according to one embodiment of the present application;

[0032] Figure 14 The present invention provides a flow chart of an oscillating redox power generation method according to an embodiment of the present application.

[0033] Explanation of the accompanying drawings: 100-first electrode, 110-first current collector, 120-first electrode material, 200-second electrode, 210-second current collector, 220-second electrode material, 300-first electrolyte, 310-first solvent, 320-first redox couple, 400-second electrolyte, 410-second solvent, 420-second redox couple, 500-diaphragm, 600-external circuit and 10-oscillating redox power generation device. DETAILED DESCRIPTION

[0034] The following describes in detail embodiments of the present application. Examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present application, and should not be construed as limiting the present application.

[0035] In the related art, when the first electrode contacts the electrolyte, a first solid-liquid interface double layer is formed between the first electrode and the electrolyte. At this time, the first electrode has an initial potential in the electrolyte solution. When the second electrode contacts the electrolyte, a second solid-liquid interface double layer is formed between the second electrode and the electrolyte. At this time, the second electrode has an initial potential in the electrolyte. when When the first electrode and the second electrode are connected, there is a potential difference between them. Since the first electrode and the second electrode are electrically connected through an external circuit, and the external circuit is provided with a switch and a load connected in series, when the switch of the external circuit is closed, electrons will flow from the second electrode to the first electrode through the external circuit, generating a current passing through the load. and The difference between them will gradually decrease until it reaches zero.

[0036] When the switch of the external circuit is disconnected, the electrons obtained by the first electrode will dissipate into the environment, causing the electrode potential to rise until it returns to the state before the short circuit; similarly, the potential of the second electrode will gradually decrease and return to the state before the short circuit. Therefore, the material of the first electrode and the material of the second electrode are hardly consumed during the charge and discharge process. However, the recovery speed of the electrode potential after the switch is disconnected is usually much slower than the change speed of the electrode potential during the short circuit, which means that the time when the switch is disconnected is often longer than the time when the switch is closed, which limits the power generation method in practical applications.

[0037] The following describes an oscillating redox power generation device, power generation device, and power generation method according to an embodiment of the present application with reference to the accompanying drawings. In response to the problem of insufficient flexibility brought about by the equipment for special power output scenarios mentioned in the above background technology, the present application provides an oscillating redox power generation device, which, by regulating the surface properties of the electrode material and the type of electrolyte, constructs an asymmetric interface structure to achieve the generation of a potential difference between the electrodes, such as the potential difference between the first potential and the second potential. The electrode charged state induced by solid-liquid contact has good self-recovery, and the electrode potential can still be restored to the state before discharge after discharge, and the two electrodes are almost not consumed during the power generation process. Therefore, when there is a redox pair in the electrolyte, and the redox potential of the redox pair and the electrode potential conform to a specific potential distribution, during the process of short-circuiting and disconnecting the external circuit switch, the redox pair will undergo a corresponding oxidation / reduction reaction or reduction / oxidation reaction, so that the first and second redox pairs are not consumed during the power generation process; this oscillating redox reaction of the redox pair will cooperate with the power generation behavior of the potential difference between the first potential and the second potential itself to achieve enhanced power output. For example, the addition of a redox couple can slow down the rate of change of the electrode potential when the switch is closed, resulting in a higher voltage across the load under the same load; it can also speed up the recovery of the electrode potential after the switch is disconnected, allowing the device to operate at a faster switching frequency. The entire power generation process does not require pre-charging operations with an external power supply, enabling long-term cyclic power generation. The device does not rely on specific environmental conditions and allows for flexible selection of electrolytes, making it suitable for a variety of application scenarios, ranging from daily life to industrial production. This solves the problem of the high specificity of the operating environment in related technologies, which limits the flexibility and wide application of the technology.

[0038] Specifically, Figure 1 Schematic diagram of an oscillating redox power generation device according to an embodiment of the present application.

[0039] like Figure 1 As shown, the oscillating redox power generation device 10 includes: a first electrode 100 , a second electrode 200 , a first electrolyte 300 , a second electrolyte 400 , a separator 500 and an external circuit 600 .

[0040] Among them, the separator 500 is arranged between the first electrolyte 300 and the second electrolyte 400; the first electrode 100 is arranged in the first electrolyte 300, the second electrode 200 is arranged in the second electrolyte 400, and the external circuit 600 is arranged between the first electrode 100 and the second electrode 200, and the external circuit 600 includes a switch.

[0041] The first electrolyte 300 includes a first solvent 310 and a first redox couple 320, and the second electrolyte 400 includes a second solvent 410 and a second redox couple 420. The first potential of the first electrode 100 immersed in the first solvent 310 is different from the second potential of the second electrode 200 immersed in the second solvent 410. The redox potential of the first redox couple 320 is a third potential, and the redox potential of the second redox couple 420 is a fourth potential. The fifth potential of the first electrode 100 immersed in the first electrolyte 300 is determined based on the first potential and the third potential, and the sixth potential of the second electrode 200 immersed in the second electrolyte 400 is determined based on the second potential and the fourth potential.

[0042] When the external circuit is turned on, the first electrode 100 is connected to the second electrode 200, and when the external circuit 600 switch is closed, since the fifth potential is greater than the sixth potential, the first redox couple 320 undergoes a reduction reaction, and the second redox couple 420 undergoes an oxidation reaction, and the redox reaction of the asymmetric redox couple, the first potential and the second potential are asymmetric and cooperative discharge is performed; when the external circuit 600 switch is disconnected, if the first potential is restored to a state where the first potential is greater than the third potential, the first redox couple 320 undergoes an oxidation reaction, and if the second potential is restored to a state where the second potential is less than the fourth potential, the second redox couple 420 undergoes a reduction reaction, and based on the self-recovery of the first potential and the second potential, the first redox couple and the second redox couple are induced to recover to the state before the switch is closed.

[0043] It will be appreciated that in the embodiment of the present application, the first electrolyte 300 and the second electrolyte 400 are separated by a separator 500, ensuring the independence and potential for interaction between the two electrolytes. A first electrode 100 is disposed in the first electrolyte 300, while a second electrode 200 is disposed in the second electrolyte 400. The two are connected via an external circuit 600, forming a closed current loop.

[0044] When external circuit 600 is on, because the fifth potential is higher than the sixth potential, electrons flow from the second electrode to the first electrode, causing the first redox couple to undergo a reduction reaction and the second redox couple to undergo an oxidation reaction. This results in a coordinated discharge based on the redox reaction of the asymmetric redox couple and the asymmetry between the first and second potentials. When the switch is off, the spontaneous recovery of the first and second potentials causes electrons to flow in the opposite direction, causing the first redox couple to undergo an oxidation reaction and the second redox couple to undergo a reduction reaction. This results in charging based on the redox reaction and the recovered first and second potentials, thus achieving electrical energy storage.

[0045] It should be noted that the diaphragm 500 in the embodiment of the present application can effectively prevent the first electrolyte 300 from mixing with the second electrolyte 400. Reasonable selection of the diaphragm can reduce the internal resistance of the device and improve the power generation efficiency of the power generation device; the switch of the external circuit 600 includes a contact switch driven by wind energy, a temperature switch or thermal switch driven by temperature change, and a ball switch or vibration switch driven by human movement. Specifically, the switch on the external circuit 600 can be at least one of a single-pole single-throw switch, a rotary and selection switch, a wave switch, a sliding switch, a temperature and thermal switch, a timing switch and a cycle time relay.

[0046] Specifically, when the potential of the first electrode 100 immersed in the first solvent 310 is The potential of the second electrode 200 immersed in the second solvent 410 is in, The potential of the first redox couple 320 is The potential of the second redox couple 420 is in, Therefore, when the first electrode 100 is immersed in the first electrolyte 300, the potential when the solid-liquid two-phase charge transfer reaches equilibrium is in, When the second electrode 200 is immersed in the second electrolyte 400, the potential when the charge transfer reaches equilibrium is in,

[0047] The first electrode 100 and the second electrode 200 are connected via an external circuit 600, on which a switch and a load are connected in series. The output voltage of the asymmetric potential-induced oscillating redox power generation device is When the switch is closed, due to When current flows through the external circuit 600, the first redox couple 320 undergoes a reduction reaction, and the second redox couple 420 undergoes an oxidation reaction. It will rise again and return to the level before closing. Will be lowered and restored to the level before closing; when Restore to The first redox couple 320 undergoes an oxidation reaction. Restore to The second redox couple 420 undergoes a reduction reaction.

[0048] During the entire power generation process, no pre-charging operation with an external power supply is required, enabling long-term cyclic power generation. The addition of the redox couple slows the change in electrode potential when the switch is closed. Under the same load, the voltage across the load is higher. The addition of the redox couple also accelerates the recovery of the electrode potential after the switch is opened, allowing the device to operate at a faster switching frequency.

[0049] In an embodiment of the present application, the first electrode, the second electrode, the first redox couple, and the second redox couple are consumed in an amount less than a preset amount during the reaction. The preset amount may be set or calibrated. It is understood that the first electrode, the second electrode, the first redox couple, and the second redox couple are substantially not consumed during the reaction.

[0050] In the embodiments of this application, Figure 2 As shown, the first electrolyte 300 includes a first solvent 310 and a first redox couple 320 , and the second electrolyte 400 includes a second solvent 410 and a second redox couple 420 .

[0051] It can be understood that in the embodiment of the present application, the first electrolyte 300 is composed of the first solvent 310 and the first redox couple 320, while the second electrolyte 400 is composed of the second solvent 410 and the second redox couple 420, providing a basis for the redox reaction.

[0052] In the embodiment of the present application, the first solvent 310 and the second solvent 410 respectively include at least one of water, a salt solution, an acid solution, an alkaline solution, an ionic liquid, and an organic solvent.

[0053] It should be noted that the concentrations of the salt solution, acid solution, alkaline solution, and ionic liquid in the embodiments of the present application will directly affect the structure of the double layer at the electrode-electrolyte interface, thereby affecting the electrode potential and further affecting the output voltage. In addition, the concentrations of the salt solution, acid solution, alkaline solution, and ionic liquid will further affect the internal resistance of the device, thereby affecting the output current. Furthermore, the concentrations of the salt solution, acid solution, alkaline solution, and ionic liquid will affect the movement of ions in the solution, further affecting the recovery speed of the electrode potential, thereby affecting the average discharge power of the device.

[0054] In the embodiment of the present application, the first redox couple 320 and the second redox couple 420 respectively include at least one of a metal compound, a halide, and an aromatic compound.

[0055] Among them, the metal compound may include Fe 2+ / 3+ , Cr 2+ / 3+ ,[Fe(CN)6] 3- / 4- , [IrCl4] 2- / [IrCl4] 3- , [Ru(bpy)3] 2+ / 3+ , tris / bipyridine cobalt and metallocene, etc., and the halide may include I3 - / I - Br2 / Br -The aromatic compounds may include thianthrene and its derivatives, phenazine and its derivatives, phenothiazine and its derivatives, quinoline and its derivatives, phenol and its derivatives, 2,2,6,6-tetramethylpiperidin-1-yloxy derivatives, anthraquinone derivatives, anisole and dianisole, etc.

[0056] In the embodiment of the present application, the first electrode material 120 and the second electrode material 220 are the same or different, wherein, if the first electrode material 120 and the second electrode material 220 are the same, the first solvent 310 and the second solvent 410 are different; if the first electrode material 120 and the second electrode material 220 are different, the first solvent 310 and the second solvent 410 are the same or different.

[0057] It can be understood that in the embodiment of the present application, when the first electrode material 120 and the second electrode material 220 are the same, the first solvent 310 and the second solvent 410 must be different, so that an asymmetric double electric layer structure can be formed on the surfaces of the first electrode 100 and the second electrode 200, and a potential difference can be established; when the first electrode material 120 and the second electrode material 220 are different, the first solvent 310 and the second solvent 410 can be the same or different, because the difference between the first electrode material 120 and the second electrode material 220 can determine the formation of an asymmetric double electric layer structure on the surfaces of the first electrode 100 and the second electrode 200.

[0058] It should be noted that factors influencing the potential of an electrode in an electrolyte solution include the intrinsic properties of the electrode material, such as the type of functional groups, lattice defects, isomorphous substitution, the surface adsorption of the electrode material in the electrolyte solution, the type of electrolyte solution ions, the electrolyte solution ion concentration, the electrolyte solution temperature, etc. Generally, different electrode materials have different potentials in the same electrolyte, and the same electrode material also has different potentials in different electrolytes.

[0059] In the embodiments of this application, Figure 2 As shown, the first electrode 100 further includes a first current collector 110 and a first electrode material 120 , and the second electrode 200 further includes a second current collector 210 and a second electrode material 220 .

[0060] The first electrode material 120 is located at least on one side of the first current collector 110 , and the second electrode material 220 is located at least on one side of the second current collector 210 . The first current collector 110 and the second current collector 210 are respectively in the first electrolyte 300 and the second electrolyte 400 .

[0061] It can be understood that the embodiment of the present application is beneficial to improving the conductivity of the first electrode 100 by providing the first current collector 110, and is beneficial to improving the conductivity of the second electrode 200 by providing the second current collector 210, thereby improving the electrical output effect of the power generation device.

[0062] It should be noted that the first current collector 110 and the second current collector 210 exist stably in the first electrolyte 300 and the second electrolyte 400, respectively.

[0063] In the embodiment of the present application, the first electrode material 120 and the second electrode material 220 respectively include at least one of a metal element, a metal oxide, a hydroxide, a carbide, a sulfide, a nitride, a conductive polymer, and a carbon-based material.

[0064] It should be noted that the vertical distance between the first electrode 100 and the second electrode 200 is 0.01 cm to 4 cm. Keeping the vertical distance between the first electrode 100 and the second electrode 200 within the aforementioned range and maintaining a moderate vertical distance between the first electrode 100 and the second electrode 200 helps mitigate the potential short circuit risk caused by direct contact between the first electrode 100 and the second electrode 200, thereby improving the safety of the power generation device. A moderate distance reduces the internal resistance of the power generation device within the internal circuit, resulting in improved power generation efficiency.

[0065] The area of ​​the first electrode 100 is 0.25 cm 2 ~9cm 2 The larger the area of ​​the first electrode 100, the greater the output current. A moderate area of ​​the first electrode 100 is beneficial to ensuring the uniformity of the first electrode material 120 and the safety of the power generation device.

[0066] The area of ​​the second electrode 200 is 0.25 cm 2 ~9cm 2 The larger the area of ​​the second electrode, the greater the output current. The moderate area of ​​the second electrode 200 is conducive to ensuring the uniformity of the second electrode material 220 and the safety of the power generation device.

[0067] The thickness of the first electrode material 120 on the first electrode 100 is 5 μm to 100 μm, which can increase the storage sites at the interface of the first electrode 100 and reduce the ion migration resistance, thereby improving the device performance.

[0068] The thickness of the second electrode material 220 on the second electrode 200 is 5 μm to 100 μm, which can increase the storage sites at the interface of the second electrode 200 and reduce the ion migration resistance, thereby improving the device performance.

[0069] In the embodiment of the present application, the first current collector 110 and the second current collector 210 respectively include at least one of graphite foil, aluminum foil, copper foil, and carbon cloth.

[0070] According to the oscillating redox power generation device proposed in the embodiment of the present application, by regulating the surface properties of the electrode material and the type of electrolyte, an asymmetric interface structure is constructed to achieve the generation of a potential difference between the electrodes, such as the potential difference between the first potential and the second potential. The electrode charge state induced by solid-liquid contact has good self-recovery, and the electrode potential can still be restored to the state before discharge after discharge, and the two electrodes are almost not consumed during the power generation process. Therefore, when there is a redox pair in the electrolyte, and the redox potential of the redox pair and the electrode potential conform to a specific potential distribution, during the process of short-circuiting and disconnecting the external circuit switch, the redox pair will undergo a corresponding oxidation / reduction reaction or reduction / oxidation reaction, so that the first and second redox pairs are not consumed during the power generation process; this oscillating redox reaction of the redox pair will cooperate with the power generation behavior of the potential difference between the first potential and the second potential itself to achieve enhanced power output. For example, the addition of a redox couple can slow down the rate of change of the electrode potential when the switch is closed, resulting in a higher voltage across the load under the same load; it can also speed up the recovery of the electrode potential after the switch is disconnected, allowing the device to operate at a faster switching frequency. The entire power generation process does not require pre-charging operations with an external power supply, enabling long-term cyclic power generation. The device does not rely on specific environmental conditions and allows for flexible selection of electrolytes, making it suitable for a variety of application scenarios, ranging from daily life to industrial production. This solves the problem of the high specificity of the operating environment in related technologies, which limits the flexibility and wide application of the technology.

[0071] The preparation method of the oscillating redox power generation device is described below.

[0072] S1: In the presence of an organic solvent, an electrode material, a binder and an additive are mixed to obtain an electrode slurry.

[0073] When the electrode material is the first electrode material, the electrode slurry obtained is the first electrode material slurry; when the electrode material is the second electrode material, the electrode slurry obtained is the second electrode material slurry.

[0074] Wherein, the organic solvent includes N-methylpyrrolidone.

[0075] Wherein, the binder includes polyvinylidene fluoride, carboxymethyl cellulose or styrene-butadiene rubber emulsion.

[0076] The additives include porous carbon black, carbon nanotubes or graphene.

[0077] The mass ratio of the electrode material, the binder and the additive may be (7-9): (2-0.5): (1-0.5).

[0078] In the embodiment of the present application, the mass ratio of the first electrochemically active material, the first conductive agent and the first binder is within the above range, which can ensure the function of the electrochemically active material while improving the electronic conductivity of the interface layer and the adhesion to the first electrode layer.

[0079] S2: forming the electrode slurry on the surface of the current collector and drying it to obtain the electrode.

[0080] When the electrode slurry is a first electrode material slurry, the first electrode 100 is obtained after drying; when the electrode slurry is a second electrode material slurry, the second electrode 200 is obtained after drying.

[0081] The electrode slurry is dried at a temperature of 50° C. to 70° C. and for a time of 8 to 12 hours, thereby obtaining electrodes of better quality.

[0082] The electrode slurry is formed on the surface of the current collector by at least one of spraying, scraping, brushing and dipping.

[0083] In the dried electrode, the thickness of the electrode film layer on the current collector surface is 5 μm to 100 μm. Controlling the electrode film layer thickness on the current collector surface within the aforementioned range results in a moderate electrode film thickness, a low internal resistance of the electrode, and a low internal resistance of the power generation device in the internal circuit, which is beneficial for improving the power generation efficiency of the power generation device.

[0084] S3: Immerse the first electrode 100 and the second electrode 200 in the first electrolyte 300 and the second electrolyte 400 respectively, and separate the first electrolyte 300 and the second electrolyte 400 by the separator 500. The external circuit 600 is provided with a switch and a load connected in series.

[0085] The diaphragm 500 is Nafion 115, Nafion 117 or a bipolar membrane.

[0086] Specifically, if graphite foil is selected as the first current collector, the first electrode material is directly coated on the first electrode layer by a scraper, and the preparation steps are as follows:

[0087] Step 11: Select MnO2 nanoparticles as the first electrode material, Super P as the conductive agent, and polyvinylidene fluoride as the binder.

[0088] Step 12: Dissolve 10 g of polyvinylidene fluoride in 500 ml of N-methylpyrrolidone and stir magnetically at room temperature for 24 hours to obtain a binder slurry.

[0089] Step 13: Mix 10 wt% of MnO2 nanoparticles, 20 wt% of Super P and 10 wt% of polyvinylidene fluoride to prepare an electrode material slurry.

[0090] A 100 μm scraper was used to apply the electrode material slurry onto graphite foil and dried in a 60°C oven to obtain a first electrode material supported on a first current collector, designated as a MnO2 electrode. The dried first electrode material had a thickness of 12 μm.

[0091] If graphite foil is selected as the second current collector, the second electrode material is directly coated on the second current collector by scraping with a scraper. The preparation steps are as follows:

[0092] Step 21: Select MoS2 nanosheets as the second electrode material, Super P as the conductive agent, and polyvinylidene fluoride as the binder;

[0093] Step 22: dissolving 10 g of polyvinylidene fluoride in 500 ml of N-methylpyrrolidone and magnetically stirring at room temperature for 24 hours to obtain a binder slurry;

[0094] Step 23, preparing an electrode material slurry by mixing 10 wt% of MoS2 nanosheets, 20 wt% of Super P and 10 wt% of polyvinylidene fluoride;

[0095] A 100 μm scraper was used to scrape the electrode material slurry onto graphite foil and dried in an oven at 60°C to obtain a second electrode material supported on a second current collector, designated as a MoS2 electrode. The dried second electrode material had a thickness of 12 μm.

[0096] I2 / KI was selected as the first redox couple, 0.1 M KCl was selected as the first solvent, and the first electrolyte was a 0.1 M KCl aqueous solution containing 1.25 mM I2 and 5 mM KI.

[0097] K3[Fe(CN)6] / K4[Fe(CN)6] was selected as the second redox couple, 0.1M KCl was used as the first solvent, and the first electrolyte was a 0.1M KCl aqueous solution containing 5mM K3[Fe(CN)6] and 5mM K4[Fe(CN)6].

[0098] The first electrolyte and the second electrolyte were separated by Nafion115, and a MnO2 electrode was inserted into the first electrolyte, and a MoS2 electrode was inserted into the second electrolyte. The distance between the first electrode and the second electrode was 4 cm to prepare an asymmetric potential-induced oscillating redox power generation device.

[0099] Among them, the asymmetric surface charge of MnO2 electrode and MoS2 electrode has an impact on the potential of MnO2 electrode. and MoS2 electrode potential The impact of Figure 3As shown in the figure, the zeta potential of the MnO2 electrode is 31mV, and the zeta potential of the MoS2 electrode is -9mV, which indicates that when the MnO2 electrode is placed in the first solvent, the surface hydroxyl groups mainly undergo protonation reaction, the electrode is positively charged, and the electrode potential is is 0.84V, such as Figure 4 When the MoS2 electrode is placed in the second solvent, the surface hydroxyl groups mainly undergo deprotonation reaction, the electrode is negatively charged, and the electrode potential is 0.39V.

[0100] It should be noted that the first solvent and the second solvent here are the same, both are 0.1 M KCl solution.

[0101] In particular, the MnO2 electrode potential and MoS2 electrode potential The periodic reversible change of Figure 5 As shown in Figure 2, when the MnO2 electrode is immersed in 0.1M KCl solution and the MoS2 electrode is immersed in 0.1M KCl solution, the open circuit voltage is 0.44V. When the external circuit switch is closed for 2s to output electricity, the output current is 0.28mA cm -2 When the external circuit switch is disconnected for 20 minutes, it can be seen that the open circuit voltage can be restored to the level before closing, and there is no decay within 200 hours.

[0102] Redox potential of I2 / KI and the redox potential of K3[Fe(CN)6] / K4[Fe(CN)6] like Figure 6 As shown, the redox potential of I2 / KI The redox potential of K3[Fe(CN)6] / K4[Fe(CN)6] is 0.65V. is 0.43V.

[0103] Electrode potential of MnO2 electrode in the first electrolyte and the electrode potential of the MoS2 electrode in the second electrolyte like Figure 7 As shown, the electrode potential of the MnO2 electrode in the first electrolyte is The electrode potential of the MoS2 electrode in the second electrolyte is 0.66V. is 0.42V.

[0104] The electrical output performance of asymmetric potential-induced oscillatory redox power generation devices, such as Figure 8 As shown, the open circuit voltage is 0.24 V and the short circuit current is 1.2 mA cm -2The performance can still maintain 83% after 35 days of continuous output, and the cumulative discharge capacity after 60 days of continuous output reaches 17.5C, which far exceeds the theoretical amount of electricity that can be released by the single-direction reaction of I2 / KI and K3[Fe(CN)6] / K4[Fe(CN)6]. Figure 9 As shown, the maximum output power under load is 0.40Wm -2 At this time, the voltage on the load is 0.12V and the current is 0.33mAcm -2 , releasing energy 3.85mJ m -2 .

[0105] In addition, the first electrolyte solution is dripped onto the cellulose paper, which is recorded as the first cellulose paper. The second electrolyte solution is dripped onto the cellulose paper, which is recorded as the second cellulose paper. Figure 10 As shown, the MnO2 electrode, the first cellulose paper, Nafion115, the second cellulose paper, and the MoS2 electrode are stacked in sequence and encapsulated with polyimide tape to prepare a flexible asymmetric potential-induced oscillating redox power generation device. Figure 11 As shown, the flexible device has good integration performance, the open circuit voltage of 7 device units in series is 2V, and the short circuit current of 7 device units in parallel is 12mA.

[0106] like Figure 12 As shown in the figure, the increase in the thickness of the MoS2 electrode will increase the storage sites of interface ions, so the output current will increase, but the continuous increase in thickness will increase the internal resistance of the electrode, which is not conducive to the generation of electrical energy.

[0107] like Figure 13 As shown in the figure, an increase in KCl concentration reduces the internal resistance of the device, which is beneficial to the increase of output current. However, it also reduces the potential of the MnO2 electrode and increases the potential of the MoS2 electrode, thereby reducing the output voltage.

[0108] The present application also provides a power generation device including the above-described oscillatory redox power generation device, wherein multiple power generation devices are connected in series and / or in parallel. It is understood that the multiple power generation devices may be connected in series, in parallel, or in a combination of series and parallel power generation devices. The specific configuration may be based on actual circumstances and is not specifically limited.

[0109] Next, the oscillating redox power generation method proposed in accordance with an embodiment of the present application will be described with reference to the accompanying drawings.

[0110] Specifically, Figure 14 A schematic flow chart of an oscillating redox power generation method provided in an embodiment of the present application.

[0111] like Figure 14As shown, the oscillating redox power generation method uses the above oscillating redox power generation device to generate electricity, wherein the oscillating redox power generation method includes the following steps:

[0112] In step S101, the external circuit of the oscillating redox power generation device is controlled to be turned on, the first electrode is connected to the second electrode, and when the external circuit switch is closed, since the fifth potential is greater than the sixth potential, the first redox couple undergoes a reduction reaction and the second redox couple undergoes an oxidation reaction, and discharge is performed based on the redox reaction.

[0113] It can be understood that the embodiments of the present application precisely control the distribution of the first, second, third, and fourth potentials to ensure that the redox reaction proceeds in the desired direction in different electrolytes, thereby improving electrical output performance. Furthermore, by optimizing reaction conditions and achieving independent control, the overall stability of the system is enhanced, and the system is endowed with adaptive adjustment capabilities to cope with varying loads and environmental changes.

[0114] In step S102 , after the external circuit switch of the oscillating redox power generation device is turned off, the first potential and the second potential are respectively restored to the levels before the external circuit is turned on.

[0115] In step S103, during the recovery process of the first potential and the second potential, if the first potential is recovered to a first potential greater than the third potential, the first redox couple in the first electrolyte is induced to undergo an oxidation reaction; if the second potential is recovered to a second potential less than the fourth potential, the second redox couple in the second electrolyte is induced to undergo a reduction reaction; based on the self-recovery of the first potential and the second potential, the first redox couple and the second redox couple are induced to recover to the state before discharge.

[0116] It can be understood that the embodiment of the present application induces the oxidation reaction of the first redox couple in the first electrolyte and the reduction reaction of the second redox couple in the second electrolyte through the spontaneous recovery of the first and second potentials, successfully restoring the device to the state before power generation, enabling it to adapt to a changing energy demand environment.

[0117] It should be noted that the aforementioned explanation of the embodiment of the oscillating redox power generation device is also applicable to the oscillating redox power generation method of this embodiment, and will not be repeated here.

[0118] According to the oscillating redox power generation method proposed in the embodiment of the present application, by regulating the surface properties of the electrode material and the type of electrolyte, an asymmetric interface structure is constructed to achieve the generation of a potential difference between the electrodes, such as the potential difference between the first potential and the second potential. The electrode charge state induced by solid-liquid contact has good self-recovery, and the electrode potential can still be restored to the state before discharge after discharge, and the two electrodes are almost not consumed during the power generation process. Therefore, when there is a redox pair in the electrolyte, and the redox potential of the redox pair and the electrode potential conform to a specific potential distribution, during the process of short-circuiting and disconnecting the external circuit switch, the redox pair will undergo a corresponding oxidation / reduction reaction or reduction / oxidation reaction, so that the first and second redox pairs are not consumed during the power generation process; this oscillating redox reaction of the redox pair will cooperate with the power generation behavior of the potential difference between the first potential and the second potential itself to achieve enhanced power output. For example, the addition of a redox couple can slow down the rate of change of the electrode potential when the switch is closed, resulting in a higher voltage across the load under the same load; it can also speed up the recovery of the electrode potential after the switch is disconnected, allowing the device to operate at a faster switching frequency. The entire power generation process does not require pre-charging operations with an external power supply, enabling long-term cyclic power generation. The device does not rely on specific environmental conditions and allows for flexible selection of electrolytes, making it suitable for a variety of application scenarios, ranging from daily life to industrial production. This solves the problem of the high specificity of the operating environment in related technologies, which limits the flexibility and wide application of the technology.

[0119] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or N embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0120] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be understood to indicate or imply relative importance or implicitly specify the number of technical features indicated. Thus, a feature specified as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of this application, "N" means at least two, for example, two, three, etc., unless otherwise specifically defined.

[0121] Any process or method description in a flowchart or otherwise described herein may be understood to represent a module, fragment or portion of code comprising one or N executable instructions for implementing a custom logical function or process step, and the scope of the preferred embodiments of the present application includes alternative implementations in which functions may be performed in a different order than shown or discussed, including performing functions in a substantially simultaneous manner or in a reverse order depending on the functions involved, which should be understood by those skilled in the art to which the embodiments of the present application pertain.

[0122] It should be understood that various parts of the present application can be implemented using hardware, software, firmware, or a combination thereof. In the above-described embodiments, the steps or methods can be implemented using software or firmware stored in a memory and executed by a suitable instruction execution system. For example, if implemented using hardware, as in another embodiment, any one of the following technologies known in the art or a combination thereof can be used to implement the method: a discrete logic circuit having a logic gate circuit for implementing a logic function on a data signal, an application-specific integrated circuit having a suitable combination of logic gate circuits, a programmable gate array, a field programmable gate array, etc.

[0123] A person skilled in the art may understand that all or part of the steps carried out in the method for implementing the above-mentioned embodiment may be completed by instructing the relevant hardware through a program, and the above-mentioned program may be stored in a computer-readable storage medium, which, when executed, includes one of the steps of the method embodiment or a combination thereof.

[0124] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limitations on the present application. Ordinary technicians in this field can change, modify, replace and modify the above embodiments within the scope of the present application.

Claims

1. An oscillating redox power generation device, characterized in that: include: a first electrolyte and a second electrolyte; a separator disposed between the first electrolyte and the second electrolyte; A first electrode disposed in the first electrolyte, a second electrode disposed in the second electrolyte, and an external circuit disposed between the first electrode and the second electrode, the external circuit including a switch, wherein: The first electrolyte comprises a first solvent and a first redox couple, the second electrolyte comprises a second solvent and a second redox couple, a first potential of the first electrode immersed in the first solvent is different from a second potential of the second electrode immersed in the second solvent, a third redox potential of the first redox couple is different from a fourth redox potential of the second redox couple, a fifth potential of the first electrode immersed in the first electrolyte is determined based on the first potential and the third potential, and a sixth potential of the second electrode immersed in the second electrolyte is determined based on the second potential and the fourth potential; When the external circuit is turned on, the first electrode is connected to the second electrode, and when the external circuit switch is closed, since the fifth potential is greater than the sixth potential, the first redox couple undergoes a reduction reaction, and the second redox couple undergoes an oxidation reaction, and based on the redox reaction of the asymmetric redox couple, the first potential and the second potential are asymmetric and cooperatively discharged; when the external circuit switch is disconnected, the first potential is restored to a state where the first potential is greater than the third potential, then the first redox couple undergoes an oxidation reaction, and the second potential is restored to a state where the second potential is less than the fourth potential, then the second redox couple undergoes a reduction reaction, and based on the self-recovery of the first potential and the second potential, the first redox couple and the second redox couple are induced to recover to the state before discharge.

2. The oscillating redox power generation device according to claim 1, characterized in that The consumption of the first electrode, the second electrode, the first redox couple, and the second redox couple in the reaction is less than a preset amount.

3. The oscillating redox power generation device according to claim 2, characterized in that: The first solvent and the second solvent respectively include at least one of water, salt solution, acid solution, alkaline solution, ionic liquid, and organic solvent.

4. The oscillating redox power generation device according to claim 2, characterized in that The first redox couple and the second redox couple each include at least one of a metal compound, a halide, and an aromatic compound.

5. The oscillating redox power generation device according to claim 2, characterized in that: The material of the first electrode is the same as or different from the material of the second electrode, wherein: If the material of the first electrode is the same as the material of the second electrode, then the first solvent and the second solvent are different; If the material of the first electrode is different from the material of the second electrode, the first solvent and the second solvent are the same or different.

6. The oscillating redox power generation device according to claim 1, characterized in that The first electrode further includes a first current collector, and the second electrode further includes a second current collector. The material of the first electrode is located on at least one side of the first current collector, and the material of the second electrode is located on at least one side of the second current collector. The first current collector and the second current collector are respectively in the first electrolyte and the second electrolyte.

7. The oscillating redox power generation device according to claim 1 or 6, characterized in that: The material of the first electrode and the material of the second electrode respectively include at least one of a metal element, a metal oxide, a hydroxide, a carbide, a sulfide, a nitride, a conductive polymer, and a carbon-based material.

8. The oscillating redox power generation device according to claim 6, characterized in that The first current collector and the second current collector respectively include at least one of graphite foil, aluminum foil, copper foil, and carbon cloth.

9. A power generation device, characterized in that: It comprises a plurality of oscillating redox power generation devices according to any one of claims 1 to 8, wherein the plurality of power generation devices are connected in series and / or in parallel.

10. An oscillating redox power generation method, characterized in that: The method uses the oscillating redox power generation device according to any one of claims 1 to 8 to generate electricity, wherein the method comprises the following steps: Controlling the external circuit of the oscillating redox power generation device to be turned on, connecting the first electrode to the second electrode, and when the external circuit switch is closed, since the fifth potential is greater than the sixth potential, the first redox couple undergoes a reduction reaction, and the second redox couple undergoes an oxidation reaction, thereby achieving coordinated discharge based on the redox reaction of the asymmetric redox couple and the asymmetry between the first potential and the second potential; After the external circuit switch of the oscillating redox power generation device is turned off, the first potential and the second potential are respectively restored to the levels before the external circuit is turned on; During the recovery process of the first potential and the second potential, if the first potential is recovered to the point where the first potential is greater than the third potential, the first redox couple in the first electrolyte is induced to undergo an oxidation reaction; if the second potential is recovered to the point where the second potential is less than the fourth potential, the second redox couple in the second electrolyte is induced to undergo a reduction reaction; based on the self-recovery of the first potential and the second potential, the first redox couple and the second redox couple are induced to recover to the state before discharge.

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