Oscillation oxidation reduction power generation device, power generation device and power generation method

Abstract

The invention relates to the technical field of new energy, in particular to an oscillation oxidation reduction power generation device, a power generation device and a power generation method. The diaphragm is arranged between the first electrolyte and the second electrolyte; the first electrode is arranged in the first electrolyte; the second electrode is arranged in the second electrolyte; the external circuit is arranged between the first electrode and the second electrode; when the external circuit is conducted, the first electrode is connected with the second electrode, the first redox couple is subjected to a reduction reaction and the second redox couple is subjected to an oxidation reaction due to the fact that the fifth potential is larger than the sixth potential; when the external circuit is disconnected, the first potential is recovered to be larger than the third potential, the first redox couple is subjected to an oxidation reaction, the second potential is recovered to be smaller than the fourth potential, and the second redox couple is subjected to a reduction reaction. Therefore, the problems that the flexibility and wide application of the technology are limited due to the specificity of the operating environment in the related technology are solved.

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 device and a power generation method. Background Art

[0002] Energy is the cornerstone of social progress and its importance is irreplaceable. With the energy depletion crisis and global warming caused by the widespread use of fossil energy becoming increasingly severe, human society is standing at a critical juncture of energy transformation. In this context, exploring and developing sustainable green energy has become a major mission of the times.

[0003] In recent years, the scientific research community has made significant progress in the field of green energy, and a series of cutting-edge power generation technologies such as piezoelectricity, friction, thermoelectricity, moisture, hydrovoltaic and osmotic power generation have been introduced. These technologies are based on unique physical effects or natural phenomena, and have achieved the goal of directly capturing energy from the environment and converting it into electrical energy, showing great environmental protection potential and application prospects. However, these emerging technologies are often limited to specific operating environments, such as light, temperature, humidity or salinity, which to some extent limits the flexibility and popularity of their applications. 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] In a first aspect, an embodiment of the present application provides an oscillating redox power generation device, comprising: a first electrolyte and a second electrolyte; a diaphragm 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 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 redox 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 provided, and a sixth potential of the second electrode immersed in the second electrolyte is determined according to 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 asymmetrically coordinated for discharge; when the external circuit 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 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 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 respectively in the first electrolyte and the second electrolyte.

[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 an oscillating redox power generation device as described above, 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 generates electricity using the above oscillating redox power generation device, 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 pair undergoes a reduction reaction, and the second redox pair undergoes an oxidation reaction, and the redox reaction of the asymmetric redox pair, the first potential and the second potential are asymmetrically coordinated for discharge; 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 a state where the first potential is greater than the third potential, the first redox pair in the first electrolyte is induced to undergo 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 pair 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 pair and the second redox pair are induced to recover to the state before the switch is closed.

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

[0016] The embodiments of the present application achieve the generation of potential difference between electrodes by regulating the surface characteristics of electrode materials and the type of electrolyte, constructing an asymmetric interface structure, such as the potential difference between the first potential and the second potential. The charged state of the electrode 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 and electrode potential of the redox pair 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, so that the voltage across the load is higher under the same load; it can 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, and can achieve long-term cyclic power generation; the device does not rely on specific environmental conditions and allows 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 the 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 exemplary 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 A 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 provided according to one embodiment of the present application;

[0023] Figure 5 A 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 provided according to one embodiment of the present application;

[0024] Figure 6 A schematic diagram of the redox potentials of I2 / KI and K3[Fe(CN)6] / K4[Fe(CN)6] provided 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 an embodiment of the present application;

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

[0028] Fig.10 A schematic diagram of the structure of a device provided according to an embodiment of the present application;

[0029] Fig.11 A schematic diagram of the integrated performance of a device provided according to an embodiment of the present application;

[0030] Fig.12 A schematic diagram of electrical output performance at different MoS2 electrode thicknesses provided according to an embodiment of the present application;

[0031] Fig.13 A schematic diagram of electrical output performance under different KCl concentrations provided according to an embodiment of the present application;

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

[0033] Explanation of the reference numerals: 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 embodiments of the present application are described in detail below, and 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 a switch and a load are connected in series on the external circuit, 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 charging and discharging 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 the oscillating redox power generation device, power generation device and power generation method of the embodiment of the present application with reference to the accompanying drawings. In view of the problem of insufficient flexibility brought 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 constructs an asymmetric interface structure by regulating the surface characteristics of the electrode material and the type of electrolyte to achieve the generation of the potential difference between the electrodes, such as the potential difference between the first potential and the second potential. The electrode charged state induced by the solid-liquid contact has good self-recovery, and the electrode potential can still be restored to 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 and electrode potential of the redox pair meet the 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, so that the voltage across the load is higher under the same load; it can 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, and can achieve long-term cyclic power generation; the device does not rely on specific environmental conditions and allows flexible selection of electrolytes, making it suitable for a variety of application scenarios, ranging from daily life to industrial production. This solves the problems of high specificity of the operating environment in related technologies, which limits the flexibility and wide application of the technology.

[0038] Specifically, Figure 1 It is a block 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 diaphragm 500 and an external circuit 600 .

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

[0041] The first electrolyte 300 comprises a first solvent 310 and a first redox couple 320, the second electrolyte 400 comprises a second solvent 410 and a second redox couple 420, a first potential of the first electrode 100 immersed in the first solvent 310 is different from a 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, a fifth potential of the first electrode 100 immersed in the first electrolyte 300 is determined according to the first potential and the third potential, and a sixth potential of the second electrode 200 immersed in the second electrolyte 400 is determined according to 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 switch of the external circuit 600 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 cooperatively discharged; when the switch of the external circuit 600 is opened, 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 is understandable that in the embodiment of the present application, the first electrolyte 300 and the second electrolyte 400 are separated by the diaphragm 500, which ensures the independence and possibility of interaction between the two electrolytes. A first electrode 100 is provided in the first electrolyte 300, and a second electrode 200 is provided in the second electrolyte 400, and the two are connected through an external circuit 600 to form a closed current loop.

[0044] When the external circuit 600 is turned on, since the fifth potential is higher than the sixth potential, electrons flow from the second electrode to the first electrode, 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 cooperatively discharged. When the switch is turned off, the electrons flow in the opposite direction through the spontaneous recovery of the first and second potentials, the first redox couple undergoes an oxidation reaction, and the second redox couple undergoes a reduction reaction, and charging is performed based on the redox reaction, the first potential and the second potential after recovery, to achieve storage of electrical energy.

[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 changes, 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, and a switch and a load are provided in series on the external circuit 600; the output voltage of the asymmetric potential induced oscillating redox power generation device is When the switch is closed, due to When a 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; when the switch is disconnected, 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 of an external power supply is required, and long-term cycle power generation can be achieved; the addition of the redox couple can slow down the change rate of the electrode potential when the switch is closed. Under the same load, the voltage across the load is higher. The addition of the redox couple can also speed up the recovery speed of the electrode potential after the switch is disconnected, allowing the device to operate at a faster switching frequency.

[0049] In an embodiment of the present application, 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. The preset amount can be set or calibrated, and it can be understood that the first electrode, the second electrode, the first redox couple, and the second redox couple are hardly consumed during the reaction.

[0050] In the embodiments of the present 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 electric 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. Further, 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 compounds, 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 is the same as or different from the second electrode material 220, wherein if the first electrode material 120 is the same as the second electrode material 220, the first solvent 310 is different from the second solvent 410; if the first electrode material 120 is different from the second electrode material 220, the first solvent 310 is the same as or different from the second solvent 410.

[0057] It can be understood that in the embodiment of the present application, when the first electrode material 120 is the same as the second electrode material 220, 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 is different from the second electrode material 220, 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 the factors affecting the potential of the electrode in the electrolyte solution include the intrinsic properties of the electrode material, such as the type of functional group, lattice defects, isomorphous substitution, etc., 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. In general, 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 the present 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 at least located on one side of the first current collector 110 , and the second electrode material 220 is at least located 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. The vertical distance between the first electrode 100 and the second electrode 200 is controlled within the aforementioned range, and the vertical distance between the first electrode 100 and the second electrode 200 is moderate, which is conducive to alleviating the hidden danger of short circuit in the power generation device due to direct contact between the first electrode 100 and the second electrode 200, thereby improving the safety of the power generation device. When the distance is moderate, the internal resistance of the power generation device in the internal circuit is small, and the power generation efficiency of the power generation device is better.

[0065] The area of ​​the first electrode 100 is 0.25 cm 2 ~9cm 2 The larger the area of ​​the first electrode 100 is, the larger the output current is. The moderate area of ​​the first electrode 100 is conducive 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. On the one hand, the storage sites at the interface of the first electrode 100 can be increased, and at the same time, the ion migration resistance can be reduced, which is beneficial to the improvement of device performance.

[0068] The thickness of the second electrode material 220 on the second electrode 200 is 5 μm to 100 μm. On the one hand, the storage sites at the interface of the second electrode 200 can be increased, and at the same time, the ion migration resistance can be reduced, which is beneficial to the improvement of 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 characteristics 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 charged state of the electrode 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 and electrode potential of the redox pair 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, so that the voltage across the load is higher under the same load; it can 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, and can achieve long-term cyclic power generation; the device does not rely on specific environmental conditions and allows flexible selection of electrolytes, making it suitable for a variety of application scenarios, ranging from daily life to industrial production. This solves the problems of 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, as follows:

[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] Among them, when the electrode material is the first electrode material, the electrode slurry obtained at this time is the first electrode material slurry; when the electrode material is the second electrode material, the electrode slurry obtained at this time 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 latex.

[0076] Among them, 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 improve the electronic conductivity of the interface layer and the adhesion with the first electrode layer while ensuring the function of the electrochemically active material.

[0079] S2: forming the electrode slurry on the surface of the current collector and obtaining the electrode after drying.

[0080] When the electrode slurry is a first electrode material slurry, a first electrode 100 is obtained after drying; when the electrode slurry is a second electrode material slurry, a 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 an electrode of good 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] Among them, in the electrode obtained by drying, the thickness of the electrode film layer on the surface of the current collector is 5μm to 100μm. When the thickness of the electrode film layer on the surface of the current collector is controlled within the aforementioned range, the thickness of the electrode film layer is moderate, the internal resistance of the electrode is small, and the internal resistance of the power generation device in the internal circuit is small, which is conducive to improving the power generation efficiency of the power generation device.

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

[0085] The membrane 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 selected to scrape the electrode material slurry onto the graphite foil and dried in an oven at 60° C. to obtain a first electrode material supported on the first current collector, which was recorded as MnO2 electrode. The thickness of the dried first electrode material was 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, selecting 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, mixing 10wt% MoS2 nanosheets, 20wt% Super P and 10wt% polyvinylidene fluoride to prepare an electrode material slurry;

[0095] A 100 μm scraper was selected to scrape the electrode material slurry onto the graphite foil and dried in an oven at 60° C. to obtain a second electrode material supported on the second current collector, which was recorded as MoS2 electrode. The second electrode material after drying was 12 μm.

[0096] I2 / KI was selected as the first redox couple, 0.1M KCl was selected as the first solvent, and the first electrolyte was a 0.1M KCl aqueous solution containing 1.25mMI2 and 5mM KI.

[0097] K3[Fe(CN)6] / K4[Fe(CN)6] was selected as the second redox couple, 0.1M KCl was selected 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 are separated by Nafion115, the MnO2 electrode is inserted into the first electrolyte, the MoS2 electrode is inserted into the second electrolyte, the distance between the first electrode and the second electrode is 4 cm, and an asymmetric potential-induced oscillating redox power generation device is prepared.

[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 Figure 2, the zeta potential of the MnO2 electrode is 31 mV, and the zeta potential of the MoS2 electrode is -9 mV. This indicates that when the MnO2 electrode is placed in the first solvent, the surface hydroxyl groups mainly undergo protonation reactions, the electrode is positively charged, and the electrode potential 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 are the same, both of which are 0.1 M KCl solution.

[0101] In particular, the MnO2 electrode potential and MoS2 electrode potential The periodic reversible changes of Figure 5 As shown in the figure, 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, 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 0.65 V. It 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. It 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 is far more than 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]. Fig. 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 , release energy 3.85mJ m -2 .

[0105] In addition, the first electrolyte is dripped onto the cellulose paper, which is recorded as the first cellulose paper. The second electrolyte is dripped onto the cellulose paper, which is recorded as the second cellulose paper. Fig.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. Fig.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 Fig.12 As shown, 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 Fig.13 As shown in the figure, the increase of KCl concentration will reduce the internal resistance of the device, which is beneficial to the increase of output current. However, it will also reduce the potential of MnO2 electrode and increase the potential of MoS2 electrode, thus reducing the output voltage.

[0108] The present application also provides a power generation device, including the above oscillating redox power generation device, wherein multiple power generation devices are connected in series and / or in parallel. It is understandable that multiple power generation devices can be connected in series or in parallel, or there can be both series power generation devices and parallel power generation devices, which can be specifically configured according to actual conditions without specific limitation.

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

[0111] like Fig.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 is understandable that the embodiment of the present application ensures that the redox reaction proceeds in the expected direction in different electrolytes by precisely controlling the distribution of the first, second, third, and fourth potentials, thereby improving the electrical output performance. At the same time, by optimizing the reaction conditions and achieving independent control, the overall stability of the system is enhanced, and it is given the ability to adaptively adjust to cope with different loads and environmental changes.

[0114] In step S102, after the external circuit switch of the control oscillation redox power generation device is turned off, the first potential and the second potential are respectively restored to the state 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 level where the first potential is greater than the third potential, an oxidation reaction is induced in the first redox couple in the first electrolyte; if the second potential is recovered to a level where the second potential is less than the fourth potential, a reduction reaction is induced in the second redox couple in the second electrolyte; 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, thereby 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 above 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 characteristics 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 and electrode potential of the redox pair 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, so that the voltage across the load is higher under the same load; it can 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, and can achieve long-term cyclic power generation; the device does not rely on specific environmental conditions and allows flexible selection of electrolytes, making it suitable for a variety of application scenarios, ranging from daily life to industrial production. This solves the problems of 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" etc. 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 are not necessarily directed to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or N embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0120] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the features. In the description of this application, "N" means at least two, such as two, three, etc., unless otherwise clearly and 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 the steps of a custom logical function or process, and the scope of the preferred embodiments of the present application includes alternative implementations in which functions may not be performed in the order shown or discussed, including performing functions in a substantially simultaneous manner or in reverse order depending on the functions involved, which should be understood by technicians in the technical field to which the embodiments of the present application belong.

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

[0123] A person of ordinary skill in the art may understand that all or part of the steps carried by the method for implementing the above-mentioned embodiment may be completed by instructing related 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 comprising 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 for coordinated discharge; 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 respectively 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 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 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 at least located on one side of the first current collector, and the material of the second electrode is at least located on 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 as described in 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: 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 based on the redox reaction of the asymmetric redox couple, the first potential and the second potential are asymmetrically discharged in a coordinated manner; 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 state 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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