Flow type vanadium-based electric fuel energy storage and supply system

Abstract

The invention discloses a flowing type vanadium-based electric fuel energy storage and supply system which comprises an electric pile reaction module, an electrolyte driving module and a medium storage module, and the electric pile reaction module comprises an oxygen evolution reaction flowing unit, a vanadium electrolyte flowing unit and an oxygen reduction reaction flowing unit which are arranged adjacently in pairs; a first flow field plate in the oxygen evolution reaction flow unit is provided with a bionic dendritic interdigital first flow channel; a second flow field plate in the vanadium electrolyte flowing unit is provided with a bidirectional spiral interdigital second flow channel; a third flow field plate in the oxygen reduction reaction flow unit is provided with a third multi-stage fractal interdigital flow channel; the medium storage module comprises a vanadium electrolyte storage tank and a reaction medium storage tank, the vanadium electrolyte storage tank and the reaction medium storage tank are arranged on the two opposite sides of the galvanic pile reaction module, the vanadium electrolyte storage tank is connected with the second flow field plate, and the reaction medium storage tank is connected with the second flow field plate and the third flow field plate. According to the system, the integration level of the system is improved on the basis of reducing the cost.

Description

Technical Field

[0001] The present application relates to the field of electrochemical energy storage, and particularly to a flow-type vanadium-based electrofuel energy storage and supply system. Background Art

[0002] The existing vanadium-air battery has the following advantages compared with the all-vanadium redox flow battery: the energy density is doubled, and higher instantaneous power can be provided under the same volume and mass, which is suitable for high-power output scenarios; one side of the battery is replaced by air, reducing the cost of battery active materials; the working temperature range is wider and it can work normally from room temperature to 60 °C, and it can adapt to more extreme working conditions.

[0003] However, the existing vanadium-air battery uses two battery packs for charging and discharging processes respectively, with a relatively high overall system complexity and high cost, and it cannot be deployed and used in mobile energy storage devices such as electric vehicles, and the application range is relatively narrow.

[0004] Therefore, how to improve the integration of the energy storage and supply system on the basis of reducing costs so that it can be applied to the field of mobile energy storage has become an urgent problem to be solved. Summary of the Invention

[0005] The present application provides a flow-type vanadium-based electrofuel energy storage and supply system, aiming to improve the integration of the energy storage and supply system on the basis of reducing costs so that it can be applied to the field of mobile energy storage.

[0006] On the one hand, an embodiment of the present application provides a flow-type vanadium-based electrofuel energy storage and supply system, including: a stack reaction module, an electrolyte driving module, and a medium storage module. The electrolyte driving module is used to connect and drive the stack reaction module and the medium storage module to realize the charging or discharging of the energy storage and supply system; the stack reaction module includes an oxygen evolution reaction flow unit, a vanadium electrolyte flow unit, and an oxygen reduction reaction flow unit arranged adjacent to each other in pairs; the oxygen evolution reaction flow unit includes a first flow field plate, and a first flow channel is provided on the first flow field plate, and the first flow channel is a biomimetic dendritic interdigitated type; the vanadium electrolyte flow unit includes a second flow field plate, and a second flow channel is provided on the second flow field plate, and the second flow channel is a bidirectional spiral interdigitated type; the oxygen reduction reaction flow unit includes a third flow field plate, and a third flow channel is provided on the second flow field plate, and the third flow channel is a multi-level fractal interdigitated type; the medium storage module includes a vanadium electrolyte storage tank and a reaction medium storage tank, the vanadium electrolyte storage tank and the reaction medium storage tank are arranged on opposite sides of the stack reaction module, the vanadium electrolyte storage tank is connected to the second flow field plate, and the reaction medium storage tank is connected to the second flow field plate and the third flow field plate respectively.

[0007] Optionally, in some embodiments of the present application, the first flow field plate is a gradient pore structure formed by laser three-dimensional printing using a titanium alloy material, and the gradient porosity of the first flow field plate ranges from 50% to 85%.

[0008] Optionally, in some embodiments of the present application, a catalyst layer formed of iridium oxide is provided on the surface of the first flow field plate, and the loading of the catalyst layer ranges from 1.5 mg / cm² to 2.5 mg / cm².

[0009] Optionally, in some embodiments of the present application, the width of the main channel of the first flow channel is 2 mm, the width of the branch channel is 0.8 mm, and the depth of the flow channel is 1.5 mm.

[0010] Optionally, in some embodiments of the present application, the second flow field plate is prepared from graphite carbon felt, and the specific surface area of the second flow field plate is 800 m² / g.

[0011] Optionally, in some embodiments of the present application, the pitch angle of the second flow channel is 15 degrees, and the cross-sectional area of the second flow channel is 2.4 mm².

[0012] Optionally, in some embodiments of the present application, a perfluorosulfonic acid-based composite membrane is provided on the surface of the second flow field plate, and the thickness of the perfluorosulfonic acid-based composite membrane is 183 µm.

[0013] Optionally, in some embodiments of the present application, the third flow field plate is a titanium mesh, and the pore diameter of the titanium mesh is 10 µm.

[0014] Optionally, in some embodiments of the present application, a catalyst layer formed of platinum is provided on the surface of the third flow field plate, and the loading of the catalyst layer is 0.5 mg / cm².

[0015] Optionally, in some embodiments of the present application, the third flow channel includes a primary flow channel and a secondary flow channel, the width of the primary flow channel is 1.5 mm, and the width of the secondary flow channel is 0.5 mm.

[0016] Optionally, in some embodiments of the present application, the volume of the vanadium electrolyte storage tank is 5 m³, and the materials used for the inner lining of the vanadium electrolyte storage tank include fluororubber and / or silicon carbide.

[0017] Optionally, in some embodiments of the present application, the medium storage module further includes a storage tank status monitoring unit, and the storage tank status monitoring unit includes an ultrasonic concentration sensor, an on-line monitoring probe for oxidation-reduction potential, and a storage tank status sensor; wherein, the ultrasonic concentration sensor and the on-line monitoring probe for oxidation-reduction potential are disposed inside the vanadium electrolyte storage tank, and the storage tank status sensor is disposed inside the reaction medium storage tank, and the storage tank status sensor is used for monitoring the pressure, temperature and pH value inside the reaction medium storage tank.

[0018] Optionally, in some embodiments of the present application, the reaction medium storage tank stores an acidic energy storage fluid medium and a high-pressure air medium in a hierarchical manner, and the pH value of the acidic energy storage fluid medium includes 0.5.

[0019] Optionally, in some embodiments of the present application, a partition board is further disposed inside the reaction medium storage tank, the partition board is made of a nano material, and the partition board is used for separating the gas medium and the liquid medium inside the reaction medium storage tank.

[0020] Optionally, in some embodiments of the present application, the stack reaction module further includes: an ion exchange unit, a current collector unit, and a fixing unit. The ion exchange unit includes a first ion exchange membrane and a second ion exchange membrane. The first ion exchange membrane is disposed between the oxygen evolution reaction flow unit and the vanadium electrolyte flow unit, and the second ion exchange membrane is disposed between the vanadium electrolyte flow unit and the oxygen reduction reaction flow unit. The current collector unit includes a first copper plate current collector and a second copper plate current collector. The first copper plate current collector is disposed on the side of the oxygen evolution reaction flow unit away from the first ion exchange membrane, and the second copper plate current collector is disposed on the side of the oxygen reduction reaction flow unit away from the second ion exchange membrane. The fixing unit includes a first end plate and a second end plate. The first end plate is disposed on the side of the first copper plate current collector away from the oxygen evolution reaction flow unit, and the second end plate is disposed on the side of the second copper plate current collector away from the oxygen reduction reaction flow unit. The oxygen evolution reaction flow unit further includes a first sealing gasket disposed between the first flow field plate and the first ion exchange membrane. The vanadium electrolyte flow unit further includes a second sealing gasket and a third sealing gasket. The second sealing gasket is disposed between the first ion exchange membrane and the second flow field plate, and the third sealing gasket is disposed between the second flow field plate and the second ion exchange membrane. The oxygen reduction reaction flow unit further includes a fourth sealing gasket disposed between the second ion exchange membrane and the third flow field plate. The electrolyte driving module includes a battery, a first pipeline, and a second pipeline. The first pipeline is used to connect the battery to the stack reaction module, and the second pipeline is used to connect the stack reaction module to the medium storage module to charge or discharge the battery.

[0021] Compared with the prior art, the flow-type vanadium-based electrofuel energy storage and supply system provided by the present application integrates two independent battery packs required by a traditional vanadium-air battery into a single functional module by adopting a charge-discharge integrated stack reaction module, reducing the number of system components by 40% and the volume by 35%. And through the multiphase fluid cooperative regulation technology of the interdigitated flow field plate, the efficient coupling of the oxygen evolution (OER) and oxygen reduction (ORR) reactions is realized, the power density is increased to 1.8 times that of the traditional structure, and the manufacturing cost is reduced by 50% at the same time. The integration degree of the energy storage and supply system is improved on the basis of reducing the cost, so that it can be applied to the field of mobile energy storage. Description of the Drawings

[0022] Figure 1 is a schematic diagram of the flow-type vanadium-based electrofuel energy storage and supply system provided by the present application; Figure 2 is a schematic diagram of the reaction medium storage tank provided by the present application; Figure 3 is the constant voltage charging curve of the battery of the flow-type vanadium-based electrofuel energy storage and power supply system provided by this application under constant voltage charging; Figure 4 is the discharge performance curve corresponding to the constant current discharge of the flow-type vanadium-based electrofuel energy storage and power supply system provided by this application at different current densities; Figure 5 is the battery discharge performance curve of the flow-type vanadium-based electrofuel energy storage and power supply system provided by this application at different gas flow rates; Figure 6 is the battery discharge performance curve of the flow-type vanadium-based electrofuel energy storage and power supply system provided by this application at different vanadium electrolyte flow rates; Figure 7 is the battery discharge performance curve of the flow-type vanadium-based electrofuel energy storage and power supply system provided by this application at different operating temperatures. Detailed implementation manners

[0023] Next, the technical solutions in the embodiments of this application will be described with reference to the accompanying drawings in the embodiments of this application. The described technical solutions are only used to explain and illustrate the idea of this application, and should not be regarded as a limitation on the protection scope of this application.

[0024] The various embodiments provided by this application are similar, and the features in different embodiments can be combined with each other.

[0025] As Figure 1 shown, an embodiment of this application provides a flow-type vanadium-based electrofuel energy storage and power supply system, including: a stack reaction module 1, an electrolyte driving module 2, and a medium storage module 3. The electrolyte driving module 2 is used to connect and drive the stack reaction module 1 and the medium storage module 3 to realize the charging or discharging of the energy storage and power supply system.

[0026] In the embodiment of this application, the stack reaction module 1 includes an oxygen evolution reaction flow unit 10, a vanadium electrolyte flow unit 20, and an oxygen reduction reaction flow unit 30 that are arranged adjacent to each other in pairs. Preferably, the vanadium electrolyte flow unit 20 is arranged between the oxygen evolution reaction flow unit 10 and the oxygen reduction reaction flow unit 30.

[0027] Specifically, the oxygen evolution reaction (OER) flow unit 10 includes a first flow field plate 11, and a first flow channel is provided on the first flow field plate 11. The first flow channel is a biomimetic dendritic interdigitated type.

[0028] Specifically, the vanadium electrolyte flow unit 20 includes a second flow field plate 21, and a second flow channel is provided on the second flow field plate 21. The second flow channel is a bidirectional spiral interdigitated type.

[0029] Specifically, the oxygen reduction reaction (ORR) flow unit 30 includes a third flow field plate 31. A third flow channel is provided on the second flow field plate 21, and the third flow channel is a multi-level fractal interdigital type.

[0030] Specifically, the medium storage module 3 includes a vanadium electrolyte storage tank 40 and a reaction medium storage tank 50. The vanadium electrolyte storage tank 40 and the reaction medium storage tank 50 are arranged on opposite sides of the stack reaction module 1. The vanadium electrolyte storage tank 40 is connected to the second flow field plate 21, and the reaction medium storage tank 50 is connected to the second flow field plate 21 and the third flow field plate 31 respectively.

[0031] The flow-type vanadium-based electrofuel energy storage and supply system provided by the present application integrates two independent battery 24 groups required by the traditional vanadium-air battery 24 into a single functional module by adopting the charge-discharge integrated stack reaction module 1. The number of system components is reduced by 40%, and the volume is reduced by 35%. And through the multiphase fluid cooperative regulation technology of the interdigital flow field plate, the efficient coupling of the oxygen evolution (OER) and oxygen reduction (ORR) reactions is realized, the power density is increased to 1.8 times that of the traditional structure, and at the same time the manufacturing cost is reduced by 50%. It realizes the improvement of the integration degree of the energy storage and supply system on the basis of cost reduction, so that it can be applied to the field of mobile energy storage.

[0032] In the embodiment of the present application, the first flow field plate 11 is a gradient pore structure formed by laser three-dimensional printing using a titanium alloy material, and the gradient porosity of the first flow field plate 11 is between 50% and 85%. The pores on the first flow field plate 11 are distributed in a gradual change.

[0033] In the embodiment of the present application, a catalyst layer formed by iridium oxide (IrO2) is provided on the surface of the first flow field plate 11, and the loading of the catalyst layer ranges from 1.5 mg / cm² to 2.5 mg / cm². The loading of the catalyst layer includes 1.5 mg / cm², 1.6 mg / cm², 1.7 mg / cm², 1.8 mg / cm², 1.9 mg / cm², 2 mg / cm², 2.1 mg / cm², 2.2 mg / cm², 2.3 mg / cm², 2.4 mg / cm², 2.5 mg / cm². Preferably, the loading of the catalyst layer is 2 mg / cm².

[0034] In the embodiments of the present application, the value of the main channel width of the first flow channel includes 2 millimeters, the value of the branch channel width includes 0.8 millimeters, and the value of the flow channel depth includes 1.5 millimeters. Specifically, the value of the main channel width of the first flow channel includes 1.8 millimeters, 1.9 millimeters, 2 millimeters, 2.1 millimeters, 2.2 millimeters, the value of the branch channel width includes 0.6 millimeters, 0.7 millimeters, 0.8 millimeters, 0.9 millimeters, 1 millimeter, and the value of the flow channel depth includes 1.3 millimeters, 1.4 millimeters, 1.5 millimeters, 1.6 millimeters, 1.7 millimeters. Among them, the values of the main channel width, the branch channel width, and the flow channel depth of the first flow channel can be arbitrarily combined. Preferably, the value of the main channel width of the first flow channel is 2 millimeters, the value of the branch channel width is 0.8 millimeters, and the value of the flow channel depth is 1.5 millimeters (mm).

[0035] In the embodiments of the present application, by using the first flow field plate 11 made of gradient pore titanium-based by laser three-dimensional printing, with iridium oxide catalyst loaded on the surface, and the first flow channel being a bionic dendritic interdigital structure, the main channel width of the first flow channel is 2.0 millimeters, the branch channel width is 0.8 millimeters, and the depth is 1.5 millimeters, the voltage drop across the first flow channel is reduced by 52% compared to the traditional flow channel.

[0036] In the embodiments of the present application, the second flow field plate 21 is prepared from graphite carbon felt, and the value of the specific surface area of the second flow field plate 21 includes 800 square meters per gram (m² / g). The specific process includes high-temperature graphitization treatment at 2800 °C.

[0037] In the embodiments of the present application, the value of the pitch angle of the second flow channel includes 15 degrees, and the value of the cross-sectional area of the second flow channel includes 2.4 square millimeters. Specifically, the value of the pitch angle of the second flow channel includes 12 degrees, 13 degrees, 14 degrees, 15 degrees, 16 degrees, 17 degrees, 18 degrees. The value of the cross-sectional area of the second flow channel includes 2.1 square millimeters, 2.2 square millimeters, 2.3 square millimeters, 2.4 square millimeters, 2.5 square millimeters, 2.6 square millimeters, 2.7 square millimeters. Among them, the values of the pitch angle of the second flow channel and the cross-sectional area of the second flow channel can be arbitrarily combined. Preferably, the value of the pitch angle of the second flow channel is 15 degrees, and the value of the cross-sectional area of the second flow channel is 2.4 square millimeters (mm²).

[0038] In the embodiments of the present application, a perfluorosulfonic acid-based composite membrane is provided on the surface of the second flow field plate 21, and the value of the thickness of the perfluorosulfonic acid-based composite membrane includes 183 micrometers. Specifically, the value of the thickness of the perfluorosulfonic acid-based composite membrane includes 180 micrometers, 181 micrometers, 182 micrometers, 183 micrometers, 184 micrometers, 185 micrometers, 186 micrometers. Preferably, the value of the thickness of the perfluorosulfonic acid-based composite membrane is 183 micrometers (μm).

[0039] In an embodiment of the present application, the third flow field plate 31 is a titanium mesh, and the pore size of the titanium mesh includes 10 microns. Specifically, the pore size of the titanium mesh includes 8 microns, 9 microns, 10 microns, 11 microns, and 12 microns. Preferably, the pore size value of the titanium mesh is 10 microns.

[0040] In an embodiment of the present application, a catalyst layer formed of platinum (Pt) is provided on the surface of the third flow field plate 31, and the loading of the catalyst layer includes 0.5 milligrams per square centimeter. The loading of the catalyst layer includes 0.3 milligrams per square centimeter, 0.4 milligrams per square centimeter, 0.5 milligrams per square centimeter, 0.6 milligrams per square centimeter, and 0.7 milligrams per square centimeter. Preferably, the loading of the catalyst layer is 0.5 milligrams per square centimeter (mg / cm²).

[0041] In an embodiment of the present application, the third flow channel includes a primary flow channel and a secondary flow channel. The width of the primary flow channel includes 1.5 millimeters, and the width of the secondary flow channel includes 0.5 millimeters. Specifically, the width of the primary flow channel includes 1.3 millimeters, 1.4 millimeters, 1.5 millimeters, 1.6 millimeters, and 1.7 millimeters. The width of the secondary flow channel includes 0.3 millimeters, 0.4 millimeters, 0.5 millimeters, 0.6 millimeters, and 0.7 millimeters. Among them, the above-mentioned values of the width of the primary flow channel and the width of the secondary flow channel can be arbitrarily combined. Preferably, the width of the primary flow channel is 1.5 millimeters, and the width of the secondary flow channel is 0.5 millimeters.

[0042] In an embodiment of the present application, the third flow field plate 31 uses an ultra-thin microporous titanium mesh with a pore size of 10 microns. A platinum catalyst layer is provided on the surface of the titanium mesh, and the loading of platinum is 0.5 milligrams per square centimeter. Moreover, the third flow channel is a multi-level fractal interdigital type, with the width of the primary flow channel being 1.5 millimeters and the width of the secondary flow channel being 0.5 millimeters, so that the oxygen mass transfer efficiency of the third flow field plate 31 is increased to 3.8 times that of a traditional carbon paper electrode.

[0043] In an embodiment of the present application, the volume of the vanadium electrolyte storage tank 40 includes 5 cubic meters (m³), and the materials used for the inner lining of the vanadium electrolyte storage tank 40 include fluororubber and / or silicon carbide.

[0044] In an embodiment of the present application, the medium storage module 3 further includes a storage tank status monitoring unit 33. The storage tank status monitoring unit includes an ultrasonic concentration sensor, an on-line monitoring probe for redox potential, and a storage tank status sensor. Among them, an ultrasonic concentration sensor and an on-line monitoring probe for redox potential are provided in the vanadium electrolyte storage tank 40, and a storage tank status sensor is provided in the reaction medium storage tank 50. The storage tank status sensor is used to monitor the pressure, temperature, and pH value inside the reaction medium storage tank 50.

[0045] In an embodiment of the present application, the stack reaction module 1 further includes: an ion exchange unit 60, a current collector unit 70, and a fixing unit 80.

[0046] In an embodiment of the present application, the ion exchange unit 60 includes a first ion exchange membrane 61 and a second ion exchange membrane 62. The first ion exchange membrane 61 is disposed between the oxygen evolution reaction flow unit 10 and the vanadium electrolyte flow unit 20, and the second ion exchange membrane 62 is disposed between the vanadium electrolyte flow unit 20 and the oxygen reduction reaction flow unit 30.

[0047] In an embodiment of the present application, the oxygen evolution reaction flow unit 10 further includes a first sealing gasket 12, and the first sealing gasket 12 is disposed between the first flow field plate 11 and the first ion exchange membrane 61. The vanadium electrolyte flow unit 20 further includes a second sealing gasket 22 and a third sealing gasket 23. The second sealing gasket 22 is disposed between the first ion exchange membrane 61 and the second flow field plate 21, and the third sealing gasket 23 is disposed between the second flow field plate 21 and the second ion exchange membrane 62. The oxygen reduction reaction flow unit 30 further includes a fourth sealing gasket 32, and the fourth sealing gasket 32 is disposed between the second ion exchange membrane 62 and the third flow field plate 31.

[0048] In an embodiment of the present application, the current collector unit 70 includes a first copper current collector 71 and a second copper current collector 72. The first copper current collector 71 is disposed on a side of the oxygen evolution reaction flow unit 10 away from the first ion exchange membrane 61, and the second copper current collector 72 is disposed on a side of the oxygen reduction reaction flow unit 30 away from the second ion exchange membrane 62.

[0049] In an embodiment of the present application, the fixing unit 80 includes a first end plate 81 and a second end plate 82. The first end plate 81 is disposed on a side of the first copper current collector 71 away from the oxygen evolution reaction flow unit 10, and the second end plate 82 is disposed on a side of the second copper current collector 72 away from the oxygen reduction reaction flow unit 30.

[0050] In an embodiment of the present application, the electrolyte driving module 2 includes a battery 24, a first pipeline 25, and a second pipeline 26. The first pipeline 25 is used to connect the battery 24 to the stack reaction module 1, and the second pipeline 26 is used to connect the stack reaction module 1 to the medium storage module 3 to charge or discharge the battery 24. Among them, the material used for the second pipeline 26 includes polytetrafluoroethylene. The battery 24 is connected to the first copper current collector 71 and the second copper current collector 72 through the first pipeline 25. The vanadium electrolyte storage tank 40 is connected to the second flow field plate 21 through the second pipeline 26, and the reaction medium storage tank 50 is connected to the second flow field plate 21 and the third flow field plate 31 respectively through the second pipeline 26.

[0051] In an embodiment of the present application, the stack reaction module 1 is connected to the medium storage module 3 through a polytetrafluoroethylene-reinforced pipeline, and a magnetic levitation brushless electric pump is used to achieve low-energy consumption directional transportation of fluids. The entire system is integrated in a portable container, and anti-seismic brackets and temperature control interlayers are configured inside the container to meet the requirements of outdoor mobile deployment.

[0052] As Figure 2 shown, acidic energy storage fluid medium and high-pressure air medium are stored in a hierarchical manner in the reaction medium storage tank 50, and the pH value of the acidic energy storage fluid medium includes 0.5.

[0053] In an embodiment of the present application, a partition plate 51 is further provided in the reaction medium storage tank 50. The partition plate 51 is made of a nanomaterial and is used to separate the gas medium and the liquid medium in the reaction medium storage tank 50.

[0054] For the flow-type vanadium-based electrofuel energy storage and power supply system provided by the present application, under the conditions of a current density of 80 mA / cm² and a temperature of 25 °C, during the charging process, vanadium electrolyte (1M V 3+ / V 4+ sulfuric acid system) and OER medium (1.0M H2SO4) are respectively pumped into the corresponding flow channels, and the co - operation of vanadium ion reduction and oxygen evolution reaction is achieved by regulating the stack voltage (1.8V to 2.0 V). During the discharging process, ORR medium (80%O2 + 20%N2) and the reduced vanadium electrolyte react in the stack, and the energy conversion efficiency of the system reaches 91.2%.

[0055] The following non - restrictive embodiments can enable those of ordinary skill in the art to understand the present application more comprehensively, but do not limit the present application in any way.

[0056] Example 1: Constant - voltage charging of a new flow - type vanadium - based electrofuel energy storage system In this example, a constant - voltage charging performance test is carried out under standard test conditions (25 °C, atmospheric pressure). The configuration parameters are as follows: Vanadium electrolyte: 3.0M H2SO4 solution of 1.0 M V 3+ / V 4+ , with a flow rate of 40 mL / min; OER medium: 1.0 H2SO4 solution, with a flow rate of 40 mL / min; OER medium flow unit: Laser three - dimensional printed gradient - pore titanium - based flow field plate (porosity 50 - 85%, gradually changing distribution), with an IrO2 catalyst loaded on the surface (loading amount 2 mg / cm²), and the flow channel is a biomimetic dendritic interdigitated structure (main channel width 2.0mm, branch channel width 0.8 mm, depth 1.5 mm); Vanadium electrolyte flow unit: Graphitized carbon felt electrode (specific surface area 800 m² / g, graphitized at 2800 °C), the flow channel is designed as a bidirectional spiral interdigital type (pitch angle 15°, flow channel cross-sectional area 2.4 mm²), equipped with a perfluorosulfonic acid-based composite membrane (thickness 183 μm); Current collector unit: 140mm * 140mm * 1mm copper plate; Fixing unit: 140mm * 140mm * 1mm bakelite board; Charging voltage: 2.0V, constant voltage charging; Electrolyte storage tank temperature maintenance system: ±0.5 °C accuracy.

[0057] The constant voltage charging curve of the battery is as Figure 3 shown, the maximum charging current density is 120 mA / cm 2 , and after seven cycles, the charging current density remains at 50 mA / cm 2 .

[0058] Example 2: Constant current discharge of a new flow-type vanadium-based electrofuel energy storage system under different current density conditions.

[0059] In this example, the constant current discharge performance test was carried out under standard test conditions (25 °C, atmospheric pressure). The configuration parameters are as follows: Vanadium electrolyte: 1.0 M V 2+ in 3.0 M H2SO4 solution, flow rate 60 mL / min; ORR medium: High-pressure air (80% O2 + 20% N2), flow rate 100 sccm; ORR medium flow unit: Pt catalyst layer (Pt loading 0.5 mg / cm²) supported by ultra-thin microporous titanium mesh (pore size 10 μm), the flow channel is a multi-level fractal interdigital structure (width of the first-level flow channel 1.5 mm, width of the second-level flow channel 0.5 mm); Vanadium electrolyte flow unit: Graphitized carbon felt electrode (specific surface area 800 m² / g, graphitized at 2800 °C), the flow channel is designed as a bidirectional spiral interdigital type (pitch angle 15°, flow channel cross-sectional area 2.4 mm²), equipped with a perfluorosulfonic acid-based composite membrane (thickness 183 μm); Current collector unit: 140mm * 140mm * 1mm copper plate; Fixing unit: 140mm * 140mm * 1mm bakelite board; Discharge current: Discharge current density 10, 20, 30, 40, 50 mA / cm 2 , constant current discharge; Storage tank pressure maintenance system: ±0.1 kPa accuracy.

[0060] The discharge performance curve is as shown in Figure 4 and the highest discharge capacity is 24 Ah / L -1 .

[0061] Example 3: Discharge of the new flow-type vanadium-based electrofuel energy storage system battery 24 at different gas flow rates.

[0062] In this example, the polarization performance test of the electrofuel energy storage system was carried out under different gas flow rate conditions under standard test conditions (25 °C, atmospheric pressure). The configuration parameters are as follows: Vanadium electrolyte: 1.0 M V 2+ in 3.0 M H2SO4 solution with a flow rate of 40 mL / min; ORR medium: High-pressure air (80% O2 + 20% N2) with flow rates of 50, 100, 150, 200, 250, 300 sccm; ORR medium flow unit: Pt catalyst layer (Pt loading 0.5 mg / cm²) supported by an ultra-thin microporous titanium mesh (pore size 10 μm), and the flow channel is a multi-stage fractal interdigitated structure (primary flow channel width 1.5 mm, secondary flow channel width 0.5 mm); Vanadium electrolyte flow unit: Graphitized carbon felt electrode (specific surface area 800 m² / g, heat-treated at 2800 °C), the flow channel is designed as a bidirectional spiral interdigitated type (pitch angle 15°, flow channel cross-sectional area 2.4 mm²), and is equipped with a perfluorosulfonic acid-based composite membrane (thickness 183 μm); Current collector unit: 140 mm * 140 mm * 1 mm copper plate; Fixing unit: 140 mm * 140 mm * 1 mm bakelite board; Discharge current: 50, 100, 150, 200, 250, 300 mA / cm 2 , with gradient discharge; Storage tank pressure maintenance system: ±0.1 kPa accuracy.

[0063] The discharge performance curve is as shown in Figure 5 and under the condition of a flow rate of 50 sccm, the example shows a peak power density of 68 mW / cm -2 .

[0064] Example 4: Discharge of the new flow-type vanadium-based electrofuel energy storage system at different vanadium electrolyte flow rates.

[0065] In this example, the polarization performance test of the electrofuel energy storage system was carried out under different gas flow rate conditions under standard test conditions (25 °C, atmospheric pressure). The configuration parameters are as follows: Vanadium electrolyte: 1.0 M V 2+3.0 M H2SO4 solution, flow rates of 5, 10, 20, 40, 60, 80 mL / min; ORR medium: high-pressure air (80% O2 + 20% N2), flow rates of 50, 100, 150, 200, 250, 300 sccm; ORR medium flow unit: Pt catalyst layer supported by ultra-thin microporous titanium mesh (pore size 10 μm) (Pt loading 0.5 mg / cm²), flow channels with a multi-level fractal interdigitated structure (primary flow channel width 1.5 mm, secondary flow channel width 0.5 mm); Vanadium electrolyte flow unit: graphitized carbon felt electrode (specific surface area 800 m² / g, heat-treated at 2800 °C for high-temperature graphitization), flow channels designed as a bidirectional spiral interdigitated type (pitch angle 15°, flow channel cross-sectional area 2.4 mm²), paired with a perfluorosulfonic acid-based composite membrane (thickness 183 μm); Current collector unit: 140 mm * 140 mm * 1 mm copper plate; Fixing unit: 140 mm * 140 mm * 1 mm bakelite board; Discharge current: 50, 100, 150, 200, 250, 300 mA / cm 2 , gradient discharge; Storage tank pressure maintenance system: accuracy of ±0.1 kPa.

[0066] The discharge performance curve is as Figure 6 shown. Under the flow rate condition of 40 mL / min -1 , the peak power density of the example is 110.5 mW / cm -2 .

[0067] Example 5: Discharge of the new flow-type vanadium-based electrofuel energy storage system at different working temperatures.

[0068] In this example, the polarization performance test of the electrofuel energy storage system was carried out under different gas flow rate conditions under standard test conditions (atmospheric pressure). The configuration parameters are as follows: Vanadium electrolyte: 1.0 M V 2+ in 3.0 M H2SO4 solution, flow rate 40 mL / min; ORR medium: high-pressure air (80% O2 + 20% N2), flow rate 100 sccm; ORR medium flow unit: Pt catalyst layer supported by ultra-thin microporous titanium mesh (pore size 10 μm) (Pt loading 0.5 mg / cm²), flow channels with a multi-level fractal interdigitated structure (primary flow channel width 1.5 mm, secondary flow channel width 0.5 mm); Vanadium electrolyte flow unit: Graphitized carbon felt electrode (specific surface area 800 m² / g, graphitized at 2800 °C), the flow channel is designed as a bidirectional spiral interdigital type (pitch angle 15°, flow channel cross-sectional area 2.4 mm²), paired with a perfluorosulfonic acid-based composite membrane (thickness 183 μm); Current collector unit: 140mm * 140mm * 1mm copper plate; Fixing unit: 140mm * 140mm * 1mm bakelite board; Discharge current: 50, 100, 150, 200, 250, 300 mA / cm 2 , gradient discharge; Storage tank pressure maintenance system: Accuracy of ±0.1 kPa.

[0069] Operating temperature: 23 °C (room temperature), 40 °C, 50 °C, 60 °C.

[0070] The discharge performance curve is as Figure 7 shown. Under the condition of 40 °C, the peak power density of the example is 80 mW / cm -2 .

[0071] Compared with the prior art, the flow-type vanadium-based electrofuel energy storage and power supply system provided by this application has the following beneficial effects: 1. The integrated design breaks through the limitations of the traditional architecture: By adopting a charge-discharge integrated stack reaction module, the two independent battery packs required for traditional vanadium-air batteries are integrated into a single functional module. The number of system components is reduced by 40%, and the volume is reduced by 35%. And through the multiphase fluid cooperative regulation technology of the interdigital flow field plate, the efficient coupling of oxygen evolution (OER) and oxygen reduction (ORR) reactions is realized. The power density is increased to 1.8 times that of the traditional structure, and the manufacturing cost is reduced by 50%. It realizes the improvement of the integration degree of the energy storage and power supply system on the basis of cost reduction, making it applicable to the mobile energy storage field.

[0072] 2. Wide-range operating condition adaptability and application scalability: The system operates stably within a wide temperature range from room temperature to 60 °C (capacity fluctuation <5%), supports dynamic regulation of 80 - 120% of the rated power (response time <200 ms), and is especially suitable for: • Mobile energy storage: Integrated portable container (size 40 feet), supports vehicle-mounted deployment and rapid replacement.

[0073] • Grid-level frequency modulation: Has a millisecond-level power response ability, and the frequency modulation accuracy reaches 99.3%.

[0074] • Off-grid power supply system: The energy storage capacity can be expanded to 200 MWh level through multi-tank parallel connection.

[0075] 3. Intrinsic safety and environmental protection features: An all-acidic aqueous electrolyte system (pH = 0.5) is adopted to eliminate the risk of combustion and explosion of organic solvents; based on the vanadium ion valence transformation mechanism, no by-products are generated during the system cycle, and the electrolyte recovery rate > 99.5%. Equipped with an intelligent thermal runaway warning system, it can start emergency shutdown within 0.5 seconds when the temperature is abnormal (>65 °C) or the pressure changes suddenly (>10 kPa / s), and the safety factor is 3 times higher than that of the traditional system.

[0076] 4. Significant economic benefits: Through the reduction of the number of storage tanks and the optimization of material costs, the unit energy storage cost of the system is 50% lower than that of the traditional vanadium-air battery 24, and it supports on-line regeneration of the electrolyte. In the scenario of a 100 MW / 400 MWh energy storage power station, the levelized cost of electricity over the entire life cycle can be controlled at $0.045 / kWh, and the investment payback period is shortened to 5.2 years.

[0077] The above has introduced in detail a flow-type vanadium-based electrofuel energy storage and supply system described in the embodiments of the present application. The description of the above embodiments is only used to help understand the core idea of the present application, and the above description should not be construed as a limitation on the protection scope of the present application.

Claims

1. A flow-type vanadium-based electrofuel energy storage and supply system, characterized in that, Comprising: a stack reaction module, an electrolyte driving module, and a medium storage module, wherein the electrolyte driving module is used to connect and drive the stack reaction module and the medium storage module to realize charging or discharging of the energy storage and supply system; the stack reaction module includes an oxygen evolution reaction flow unit, a vanadium electrolyte flow unit, and an oxygen reduction reaction flow unit arranged adjacent to each other in pairs; the oxygen evolution reaction flow unit includes a first flow field plate, and a first flow channel is provided on the first flow field plate, and the first flow channel is a biomimetic dendritic interdigitated type; the vanadium electrolyte flow unit includes a second flow field plate, and a second flow channel is provided on the second flow field plate, and the second flow channel is a bidirectional spiral interdigitated type; the oxygen reduction reaction flow unit includes a third flow field plate, and a third flow channel is provided on the second flow field plate, and the third flow channel is a multi-level fractal interdigitated type; the medium storage module includes a vanadium electrolyte storage tank and a reaction medium storage tank, the vanadium electrolyte storage tank and the reaction medium storage tank are arranged on opposite sides of the stack reaction module, the vanadium electrolyte storage tank is connected to the second flow field plate, and the reaction medium storage tank is respectively connected to the second flow field plate and the third flow field plate.

2. The flow-type vanadium-based electrofuel energy storage and supply system according to claim 1, wherein The first flow field plate is a gradient pore structure formed by laser three-dimensional printing using a titanium alloy material, and the gradient porosity of the first flow field plate is between 50% and 85%.

3. The flow-type vanadium-based electrofuel energy storage and supply system according to claim 1 or 2, wherein A catalyst layer formed of iridium oxide is provided on the surface of the first flow field plate, and the loading of the catalyst layer ranges from 1.5 mg / cm² to 2.5 mg / cm².

4. The flow-type vanadium-based electrofuel energy storage and supply system according to claim 3, wherein, The width of the main channel of the first flow channel is 2 mm, the width of the branch channel is 0.8 mm, and the depth of the flow channel is 1.5 mm.

5. The flow-type vanadium-based electrofuel energy storage and supply system according to claim 1, wherein The second flow field plate is prepared from graphite carbon felt, and the specific surface area of the second flow field plate is 800 m² / g.

6. The flow-type vanadium-based electrofuel energy storage and supply system according to claim 1 or 5, characterized in that, The pitch angle of the second flow channel is 15°, and the cross-sectional area of the second flow channel is 2.4 mm².

7. The flow-type vanadium-based electrofuel energy storage and supply system according to claim 6, characterized in that, A perfluorosulfonic acid-based composite membrane is provided on the surface of the second flow field plate, and the thickness of the perfluorosulfonic acid-based composite membrane is 183 µm.

8. The flow-type vanadium-based electrofuel energy storage and supply system according to claim 1, wherein The third flow field plate is a titanium mesh, and the pore diameter of the titanium mesh is 10 µm.

9. The flow-type vanadium-based electrofuel energy storage and supply system according to claim 1 or 8, characterized in that, A catalyst layer formed of platinum is provided on the surface of the third flow field plate, and the loading of the catalyst layer is 0.5 mg / cm².

10. The flow-type vanadium-based electrofuel energy storage and supply system according to claim 9, wherein The third flow channel includes a primary flow channel and a secondary flow channel, the width of the primary flow channel is 1.5 mm, and the width of the secondary flow channel is 0.5 mm.

11. The flow-type vanadium-based electrofuel energy storage and supply system according to claim 1, characterized in that The volume of the vanadium electrolyte storage tank is 5 m³, and the materials used for the inner lining of the vanadium electrolyte storage tank include fluororubber and / or silicon carbide.

12. The flow-type vanadium-based electrofuel energy storage and supply system according to claim 1 or 11, characterized in that, The medium storage module further includes a storage tank state monitoring unit, and the storage tank state monitoring unit includes an ultrasonic concentration sensor, an on-line monitoring probe for oxidation-reduction potential, and a storage tank state sensor; Wherein, the ultrasonic concentration sensor and the online monitoring probe for redox potential are arranged in the vanadium electrolyte storage tank, and the storage tank state sensor is arranged in the reaction medium storage tank, and the storage tank state sensor is used to monitor the pressure, temperature and pH value inside the reaction medium storage tank.

13. The flow-type vanadium-based electrofuel energy storage and supply system according to claim 12, characterized in that, The reaction medium storage tank stores the acidic energy storage fluid medium and the high-pressure air medium in a graded manner, and the pH value of the acidic energy storage fluid medium includes 0.

5.

14. The flow-type vanadium-based electrofuel energy storage and supply system according to claim 12, characterized in that, A partition plate is further arranged in the reaction medium storage tank, the partition plate is made of a nano material, and the partition plate is used to separate the gas medium and the liquid medium in the reaction medium storage tank.

15. The flow-type vanadium-based electrofuel energy storage and supply system according to claim 1, wherein The stack reaction module further includes: An ion exchange unit, including a first ion exchange membrane and a second ion exchange membrane, the first ion exchange membrane is arranged between the oxygen evolution reaction flow unit and the vanadium electrolyte flow unit, and the second ion exchange membrane is arranged between the vanadium electrolyte flow unit and the oxygen reduction reaction flow unit; A current collector unit, including a first copper plate current collector and a second copper plate current collector, the first copper plate current collector is arranged on the side of the oxygen evolution reaction flow unit away from the first ion exchange membrane, and the second copper plate current collector is arranged on the side of the oxygen reduction reaction flow unit away from the second ion exchange membrane; A fixing unit, including a first end plate and a second end plate, the first end plate is arranged on the side of the first copper plate current collector away from the oxygen evolution reaction flow unit, and the second end plate is arranged on the side of the second copper plate current collector away from the oxygen reduction reaction flow unit; The oxygen evolution reaction flow unit further includes a first sealing gasket, and the first sealing gasket is arranged between the first flow field plate and the first ion exchange membrane; The vanadium electrolyte flow unit further includes a second sealing gasket and a third sealing gasket, the second sealing gasket is arranged between the first ion exchange membrane and the second flow field plate, and the third sealing gasket is arranged between the second flow field plate and the second ion exchange membrane; The oxygen reduction reaction flow unit further includes a fourth sealing gasket, and the fourth sealing gasket is arranged between the second ion exchange membrane and the third flow field plate; The electrolyte driving module includes a battery, a first pipeline and a second pipeline, the first pipeline is used to connect the battery and the stack reaction module, and the second pipeline is used to connect the stack reaction module and the medium storage module to charge or discharge the battery.

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