A photoelectrochemical open-circuit flow battery reactor

Abstract

The utility model discloses a kind of photoelectric open circuit flow battery reactors, including two mirror image symmetrical end plates and the anode and cathode being set between two end plates, ion exchange membrane is set between anode and cathode, anode and ion exchange membrane between and cathode and ion exchange membrane between are all set sealing plate;End plate and anode between anode side and end plate and cathode between cathode side and cathode are all set gasket;Two end plates and two gaskets are connected by bolt fastening between, and anode, sealing plate, ion exchange membrane and cathode are pressed between two gaskets.The utility model can convert closed circuit circulation redox couple into open circuit organic matter catalytic reaction and electrical energy storage by coupling photoelectrocatalytic organic matter selective oxidation reaction with flow battery energy storage process, to produce green hydrogen and high-value green chemicals, realize the efficient conversion of renewable energy to green chemicals.

Description

Technical Field

[0001] This invention belongs to the technical field of photoelectrocatalytic organic oxidation coupled flow battery energy storage reactor, specifically relating to a photoelectrocatalytic open-circuit flow battery reactor. Background Technology

[0002] Photoelectrocatalysis (PEC) is a technology that stores solar energy in the form of chemical bonds, and its research focus in the fields of clean energy conversion and green chemical synthesis has been continuously increasing in recent years. As a green chemical conversion technology that integrates light energy utilization and catalytic reaction, it has shown unique advantages in terms of energy utilization and reaction regulation: compared with the indirect conversion path of "solar energy → electrical energy → chemical energy", PEC technology completes the integrated process of "light energy absorption → charge separation → surface catalytic reaction" with the help of photoelectrodes, effectively shortening the energy conversion chain, reducing energy loss in multi-step conversion, and thus improving the theoretical energy utilization efficiency. In addition, the core advantage of photoelectrocatalysis is also reflected in the precise control of the organic oxidation pathway by controlling the band structure and surface active sites through the design of photoelectrode materials. Therefore, in the development of traditional photoelectrocatalysis systems, many studies have significantly improved the system performance through the construction of efficient organic oxidation reactions and the optimization strategy of photoelectrode materials. However, at the same time, traditional PEC systems also suffer from insufficient synergy between "light absorption-charge separation-catalytic activity" of photoelectrode materials, and require external bias voltage to promote charge separation and counteract the electron-hole recombination trend. Furthermore, the additional bias voltage typically relies on grid power, which weakens the green advantages of "solar energy utilization" and limits its application scenarios. Flow batteries, as a large-scale energy storage technology, have promising application prospects due to their advantages such as independently adjustable power capacity, long cycle life, good safety, and recyclable electrolyte; currently, their scale has reached hundreds of kilowatts to hundreds of megawatts, with energy efficiencies of 70% to 75%. For example, Qing Wang and colleagues proposed a stable and high-capacity redox-targeted electrolyte for aqueous flow batteries. Through a combination of highly stable and inexpensive ferrocyanide / ferricyanide and solid Prussian blue (PB), a capacity of 61.6 Ah L can be achieved. -1The battery boasts impressive capacity and an excellent capacity retention of 99.991% per cycle (Joule 2019, 3, 2066-2067). Zhong Jin et al. proposed a groundbreaking battery design by introducing solid-state lithium storage chemistry into aqueous redox flow batteries. By dispersing tiny lithium-storable active material particles and conductive agents into a high-salinity aqueous electrolyte, they constructed a slurry flow battery based on an interfacial charge transfer mechanism, offering advantages such as an expanded potential window, improved redox stability, and enhanced flowability. Their designed aqueous lithium-ion slurry flow battery achieves a coulombic efficiency close to 100%, long cycle life, high safety, and low system cost, showing great promise for large-scale energy storage applications (ACS Energy Letters 2022, 7, 862-870). Chunsheng Wang et al. reported a reversible chloride redox flow battery that begins with the electrolysis of an aqueous NaCl electrolyte and extracts and stores the generated Cl2 in carbon tetrachloride (CCl4) or mineral oil. A membrane-free design was achieved by utilizing the immiscibility between CCl4 or mineral oil and NaCl electrolyte, and at 10 mA / cm 2 At this level, the energy efficiency is >91%, and the energy density is 125.7 Wh / L (Nat. Commun. 2022, 13, 1281). Although these flow battery systems exhibit excellent battery performance, low energy efficiency and high cost remain pressing issues that need to be addressed. Utility Model Content

[0003] This invention is proposed to overcome the problems of high cost and low energy density of flow batteries in the prior art, and its purpose is to provide a photoelectric open-circuit flow battery reactor.

[0004] This utility model is achieved through the following technical solution:

[0005] A photoelectric open-circuit flow battery reactor includes two mirror-symmetrically arranged end plates and an anode and a cathode disposed between the two end plates. An ion exchange membrane is disposed between the anode and the cathode, and a sealing plate is disposed between the anode and the ion exchange membrane and between the cathode and the ion exchange membrane. Gaskets are disposed between the anode-side end plate and the anode, and between the cathode-side end plate and the cathode. The two end plates and the two gaskets are fastened together by bolts, pressing the anode, sealing plate, ion exchange membrane and cathode between the two gaskets.

[0006] In the above technical solution, the end plate is a plate-shaped structure, with multiple end plate fixing holes, multiple end plate positioning holes, and electrolyte inlet and electrolyte outlet arranged diagonally on the end plate; the horizontal position of the electrolyte inlet is lower than the horizontal position of the electrolyte outlet; the multiple end plate fixing holes are arranged around the end plate; the end plate positioning holes are arranged inside the end plate fixing holes; an end plate window is formed in the middle of the end plate on the anode side.

[0007] In the above technical solution, the gasket has a plate-like structure, with multiple gasket fixing holes, multiple gasket positioning holes, and gasket liquid inlets and outlets arranged diagonally on the gasket; the gasket positioning holes are arranged one-to-one with the end plate positioning holes; the gasket liquid inlets are arranged correspondingly with the electrolyte liquid inlets and are interconnected; the gasket liquid outlets are arranged correspondingly with the electrolyte liquid outlets and are interconnected; the number of gasket fixing holes is not greater than the number of end plate fixing holes, and the positions of the gasket fixing holes correspond to the positions of the end plate fixing holes; a gasket window is formed in the middle of the gasket on the anode side; the gasket window has the same size as the end plate window and is arranged in corresponding positions.

[0008] In the above technical solution, the anode is a plate-shaped structure, which includes a photoanode, an anode current collector plate and an anode flow channel plate. A sealing gasket is provided between the photoanode and the anode flow channel plate, and the anode flow channel plate is located close to the ion exchange membrane. One end of the anode current collector plate is in contact with the photoanode, and the other end is higher than the top of the end plate.

[0009] In the above technical solution, the photoanode is a plate-shaped structure with a connecting protrusion at its upper end; the photoanode is composed of a catalyst layer supported on a conductive substrate, and the catalyst layer is disposed close to the anode flow channel plate.

[0010] In the above technical solution, the anode current collector is a strip structure, wherein grooves are formed on both sides of the lower section, and the grooves divide the anode current collector into a power connection section, an embedding section and a connecting section.

[0011] In the above technical solution, the anode flow channel plate has a plate-like structure, with an anode electrolyte tank formed in the middle of the anode flow channel plate; the diagonal of the anode electrolyte tank forms an anode flow channel plate inlet and an anode flow channel plate outlet, both of which are connected to the anode electrolyte tank; the anode flow channel plate inlet and the gasket inlet are correspondingly arranged and interconnected; the anode flow channel plate outlet and the gasket outlet are correspondingly arranged and interconnected; a sealing gasket groove is formed around the anode electrolyte tank, and the sealing gasket is placed in... The anode flow channel plate is sealed within the gasket groove; a stepped groove is formed above the anode electrolyte tank, which consists of a small-diameter anode flow channel plate manifold groove and a large-diameter anode flow channel plate bare anode groove; the connecting protrusion of the bare anode is embedded in the bare anode groove of the anode flow channel plate; the embedded section of the anode manifold is embedded in the manifold groove of the anode flow channel plate, and its connecting section is embedded in the bare anode groove of the anode flow channel plate and contacts the connecting protrusion of the bare anode; multiple anode flow channel plate positioning holes are formed on both sides of the anode electrolyte tank, and the anode flow channel plate positioning holes are set one-to-one with the gasket positioning holes.

[0012] In the above technical solution, the sealing plate is a plate-shaped structure, with a catalyst groove formed in the middle of the sealing plate and multiple sealing plate positioning holes formed around the catalyst groove; the catalyst groove is a through groove, and the sealing plate positioning holes are set one-to-one with the end plate positioning holes.

[0013] In the above technical solution, the cathode includes a cathode catalyst, a cathode flow channel plate, and a cathode current collector arranged in sequence; the cathode catalyst is arranged close to the ion exchange membrane.

[0014] In the above technical solution, the cathode flow channel plate is a plate-shaped structure, in which a flow channel field is formed in the middle. The diagonals of the flow channel field form the cathode electrolyte inlet and the cathode electrolyte outlet, respectively. The cathode electrolyte inlet and the cathode electrolyte outlet are connected to the flow channel field through connecting channels. The flow channel field is a serpentine flow channel field formed by the serpentine coiling of the flow channel. The cathode catalyst is in contact with the flow channel field. Multiple cathode flow channel plate positioning holes are formed on both sides of the flow channel field, and the cathode flow channel plate positioning holes are set one-to-one with the sealing plate positioning holes. The structure of the cathode current collector plate is the same as that of the gasket on the cathode side, and the length of the cathode current collector plate is greater than that of the gasket on the cathode side.

[0015] The beneficial effects of this utility model are:

[0016] This invention provides a photoelectric open-circuit flow battery reactor. By coupling the photoelectrocatalytic selective oxidation reaction of organic matter with the flow battery energy storage process, the closed-loop redox couple can be converted into an open-circuit organic catalytic reaction and electrical energy storage to produce green hydrogen and high-value green chemicals. This achieves the efficient conversion of renewable energy into green chemicals, and utilizes additional solar energy input to reduce the energy consumption of the flow battery, improve energy efficiency, and further expand the application scenarios of photoelectrocatalytic oxidation technology. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the overall structure of this utility model;

[0018] Figure 2 This is a schematic diagram of the structure of the end plate on the anode side in this utility model;

[0019] Figure 3 This is a schematic diagram of the structure of the gasket on the anode side in this utility model;

[0020] Figure 4 This is a schematic diagram of the photoanode structure in this utility model;

[0021] Figure 5 This is a schematic diagram of the anode current collector in this utility model;

[0022] Figure 6 This is a schematic diagram of the anode flow channel plate structure in this utility model;

[0023] Figure 7 This is a schematic diagram of the sealing plate structure in this utility model;

[0024] Figure 8 This is a schematic diagram of the cathode flow channel plate structure in this utility model;

[0025] Figure 9 This is a scanning electron microscope image of the titanium dioxide semiconductor photocatalyst supported on FTO in Example 1 of this utility model;

[0026] Figure 10 This is a constant current charging diagram of hydrogen production via photoelectric open-circuit flow battery coupling in Example 1 of this utility model;

[0027] Figure 11 This is a constant current discharge diagram of the photoelectric open-circuit flow battery coupled with ethylene glycol oxidation in Example 1 of this utility model;

[0028] Figure 12 This is a constant current discharge diagram of the photoelectric open-circuit flow battery coupled with glycerol oxidation in Example 2 of this utility model;

[0029] Figure 13 This is a constant current discharge diagram of the photoelectric open-circuit flow battery coupled with benzyl alcohol oxidation in Example 3 of this utility model.

[0030] in:

[0031] 1. End plate; 11. End plate fixing hole; 12. End plate positioning hole; 13. End plate window; 14. Electrolyte inlet; 15. Electrolyte outlet;

[0032] 2. Gasket; 21. Gasket fixing hole; 22. Gasket positioning hole; 23. Gasket liquid inlet; 24. Gasket liquid outlet; 25. Gasket window;

[0033] 3. Anode; 31. Bare anode; 32. Sealing gasket; 33. Anode manifold; 34. Anode flow channel plate; 341. Anode flow channel plate positioning hole; 342. Anode flow channel plate inlet sealing ring groove; 343. Anode flow channel plate outlet sealing ring groove; 344. Anode flow channel plate inlet; 345. Anode flow channel plate outlet; 346. Anode flow channel plate sealing gasket groove; 347. Anode flow channel plate bare anode groove; 348. Anode flow channel plate manifold groove; 349. Anode electrolyte tank;

[0034] 4. Sealing plate; 41. Sealing plate positioning hole; 42. Catalyst tank;

[0035] 5. Ion exchange membrane;

[0036] 6. Cathode; 61. Cathode catalyst; 62. Cathode flow channel plate; 621. Cathode flow channel plate positioning hole; 622. Cathode electrolyte inlet; 623. Cathode electrolyte outlet; 624. Flow channel field; 63. Cathode current collector.

[0037] For those skilled in the art, other related figures can be obtained from the above figures without any creative effort. Detailed Implementation

[0038] To enable those skilled in the art to better understand the technical solution of this utility model, the technical solution of this utility model will be further described below with reference to the accompanying drawings and specific embodiments.

[0039] like Figure 1 As shown, a photoelectric open-circuit flow battery reactor includes two mirror-symmetrically arranged end plates 1 and an anode 3 and a cathode 6 disposed between the two end plates 1. An ion exchange membrane 5 is disposed between the anode 3 and the cathode 6. A sealing plate 4 is disposed between the anode 3 and the ion exchange membrane 5 and between the cathode 6 and the ion exchange membrane 5. A gasket 2 is disposed between the end plate 1 on the anode side and the anode 3, and between the end plate 1 on the cathode side and the cathode 6. The two end plates 1 and the two gaskets 2 are fastened together by bolts, which press the anode 3, the sealing plate 4, the ion exchange membrane 5 and the cathode 6 between the two gaskets 2.

[0040] like Figure 2 As shown, the end plate 1 is a plate-shaped structure, and multiple end plate fixing holes 11, multiple end plate positioning holes 12, and electrolyte inlet 14 and electrolyte outlet 15 arranged diagonally are formed on the end plate 1.

[0041] The horizontal position of the electrolyte inlet 14 is lower than that of the electrolyte outlet 15, and the electrolyte circulation follows the principle of bottom inlet and top outlet. The electrolyte inlet 14 is connected to the electrolyte outlet 15 through the anode flow channel plate 34. Multiple end plate fixing holes 11 are arranged around the end plate 1. The end plate positioning holes 12 are arranged inside the end plate fixing holes 11. An end plate window 13 is formed in the middle of the end plate 1 on the anode side. The end plate window 13 is used for lighting, and the light source shines vertically onto the photoanode 31. The light source uses a 300W xenon lamp and is equipped with an AM 1.5 G filter, with an irradiance power density of 100 mW cm⁻¹. 2 ;

[0042] The end plate 1 is made of any one of polytetrafluoroethylene, polyetheretherketone, stainless steel or aluminum plate; the thickness of the end plate 1 is 5 mm to 15 mm.

[0043] In this embodiment, eight end plate fixing holes 11 are provided on the end plate 1, and two end plate fixing holes 11 form a pair and are provided at the four corners of the end plate 1.

[0044] In this embodiment, four end plate positioning holes 12 are provided on the end plate 1; two end plate positioning holes 12 are provided on each side of the end plate window 13; the electrolyte inlet 14 and the electrolyte outlet 15 are located on the diagonal of the end plate window 13.

[0045] like Figure 3 As shown, the gasket 2 has a plate-like structure, with multiple gasket fixing holes 21, multiple gasket positioning holes 22, and gasket liquid inlets 23 and gasket liquid outlets 24 arranged diagonally on the gasket 2. The gasket positioning holes 22 correspond one-to-one with the end plate positioning holes 12. The gasket liquid inlets 23 correspond to and are interconnected with the electrolyte inlets 14. The gasket liquid outlets 24 correspond to and are interconnected with the electrolyte outlets 15. The number of gasket fixing holes 21 is no greater than the number of end plate fixing holes 11, and the positions of the gasket fixing holes 21 correspond to the positions of the end plate fixing holes 11. A gasket window 25 is formed in the middle of the gasket 2 on the anode side. The gasket window 25 has the same size as the end plate window 13 and is positioned accordingly. Sealing grooves are formed around the gasket inlets 23 and gasket outlets 24, and sealing rings are installed in the sealing grooves.

[0046] In this embodiment, the gasket 2 is provided with two gasket fixing holes 21, which are located at the two top corners of the gasket 2, and are in the same position as the end plate fixing holes 11 located at the same position.

[0047] like Figures 4-6As shown, the anode 3 has a plate-like structure, which includes a photoanode 31, an anode current collector 33, and an anode flow channel plate 34. A sealing gasket 32 ​​is provided between the photoanode 31 and the anode flow channel plate 34. The anode flow channel plate 34 is located close to the ion exchange membrane 5. One end of the anode current collector 33 is in contact with the photoanode 31, and the other end is higher than the top of the end plate 1.

[0048] like Figure 4 As shown, the photoanode 31 has a plate-like structure with a connecting protrusion at its upper end; the photoanode 31 is composed of a catalyst layer supported on a conductive substrate, and the catalyst layer is disposed close to the anode flow channel plate 34.

[0049] like Figure 5 As shown, the anode current collector 33 is a strip structure, wherein grooves are formed on both sides of the lower section, and the grooves divide the anode current collector 33 into a power connection section, an embedding section and a connecting section;

[0050] like Figure 6 As shown, the anode flow channel plate 34 has a plate-like structure, with an anode electrolyte tank 349 formed in the middle of the anode flow channel plate 349. An anode flow channel plate inlet 344 and an anode flow channel plate outlet 345 are formed along the diagonal of the anode electrolyte tank 349, both of which are connected to the anode electrolyte tank 349. The anode flow channel plate inlet 344 is correspondingly and interconnected with the gasket inlet 23. The anode flow channel plate outlet 345 is correspondingly and interconnected with the gasket outlet 24. An anode flow channel plate inlet sealing ring groove 342 is formed around the anode flow channel plate inlet 344, and a sealing ring is installed inside the anode flow channel plate inlet sealing ring groove 342. An anode flow channel plate outlet sealing ring groove 343 is formed around the anode flow channel plate outlet 345, through which the anode flow channel plate outlet... A sealing ring is installed in the sealing ring groove 343; an anode flow channel plate sealing gasket groove 346 is formed around the anode electrolyte tank 349, and a sealing gasket 32 ​​is placed in the anode flow channel plate sealing gasket groove 346; a stepped groove is formed above the anode electrolyte tank 349, which is composed of a small-diameter anode flow channel plate manifold groove 348 and a large-diameter anode flow channel plate bare anode groove 347; the connecting protrusion of the bare anode 31 is embedded in the anode flow channel plate bare anode groove 347; the embedded section of the anode manifold 33 is embedded in the anode flow channel plate manifold groove 348, and its connecting section is embedded in the anode flow channel plate bare anode groove 347 and contacts the connecting protrusion of the bare anode 31; multiple anode flow channel plate positioning holes 341 are formed on both sides of the anode electrolyte tank 349, and the anode flow channel plate positioning holes 341 are set one-to-one with the gasket positioning holes 22.

[0051] The anode flow channel plate 34 is made of any one of polytetrafluoroethylene, polyetheretherketone, stainless steel, or titanium plate; the thickness of the anode flow channel plate 34 is ≤7 mm; the depth of the anode flow channel plate inlet sealing ring groove 342 and the anode flow channel plate outlet sealing ring groove 343 is ≤3 mm; the depth of the anode flow channel plate sealing gasket groove 346 is ≤2 mm; the depth of the anode flow channel plate bare anode groove 347 is ≤3 mm; and the depth of the anode flow channel plate manifold groove 348 is ≤3 mm.

[0052] like Figure 7 As shown, the sealing plate 4 has a plate-shaped structure, with a catalyst groove 42 formed in the middle of the sealing plate 4, and multiple sealing plate positioning holes 41 formed around the catalyst groove 42; the catalyst groove 42 is a through groove, and the sealing plate positioning holes 41 are set one-to-one with the end plate positioning holes 12; the thickness of the sealing plate 4 is ≥3 mm.

[0053] The length and width of the ion exchange membrane 5 are greater than the length and width of the catalyst tank 42;

[0054] The cathode 6 includes a cathode catalyst 61, a cathode flow channel plate 62, and a cathode current collector 63 arranged sequentially; the cathode catalyst 61 is disposed close to the ion exchange membrane 5.

[0055] The cathode catalyst 61 is a platinum sheet;

[0056] like Figure 8 As shown, the cathode flow channel plate 62 has a plate-like structure, with a flow channel field 624 formed in the middle. The diagonals of the flow channel field 624 form a cathode electrolyte inlet 622 and a cathode electrolyte outlet 623, respectively. Both the cathode electrolyte inlet 622 and the cathode electrolyte outlet 623 are connected to the flow channel field 624 through connecting channels. The flow channel field 624 is a serpentine flow channel field formed by the serpentine coiling of the flow channel. The flow channel depth of the flow channel field 624 is ≤3 mm. The cathode catalyst 61 is in contact with the flow channel field 624. Multiple cathode flow channel plate positioning holes 621 are formed on both sides of the flow channel field 624, and the cathode flow channel plate positioning holes 621 are set one-to-one with the sealing plate positioning holes 41. The cathode flow channel plate 62 is made of graphite, and its thickness is ≥10 mm.

[0057] The structure of the cathode current collector 63 is the same as that of the gasket 2 on the cathode side, and the length of the cathode current collector 63 is greater than that of the gasket 2 on the cathode side.

[0058] Application Example 1

[0059] A photoelectric open-circuit flow battery reactor:

[0060] The photoanode was used as the positive electrode for charging, and the photoanode was a TiO2 catalyst supported on FTO conductive glass. The positive electrode electrolyte contained 0.2 M VO2. 2+The electrolyte is 2 M H₂SO₄; the negative electrode is a graphite felt loaded with Pt nanoparticles, which together with the 2 M H₂SO₄ electrolyte forms the negative electrode; a Nafion 117 membrane is placed between the positive and negative electrodes; the scanning electron microscope image of the TiO₂ catalyst is shown below. Figure 9 As shown, it can be seen that it has a uniform nanotube structure;

[0061] The photoanode was used as the negative electrode for discharge, and the photoanode was a TiO2 catalyst supported on FTO. The negative electrode electrolyte was a 1 M KOH electrolyte containing 0.1 M ethylene glycol organic substrate. The positive electrode for discharge was an inert graphite felt electrode containing 0.2 M VO2. + A 2 M H2SO4 electrolyte forms the positive electrode; a Nafion 117 membrane is placed between the positive and negative electrodes.

[0062] At an irradiation power density of 100 mW / cm² 2 Under a light source, the photoelectric open-circuit flow battery at 0.8 mA cm⁻¹ -2 Constant current charging is performed at the bottom, and the positive electrode will release the VO in the positive electrode electrolyte. 2+ Oxidized to VO2 + HER occurs at the negative electrode. Figure 10 At 0.8 mA cm -2 The constant-current charging curve of the open-circuit photoelectric flow battery coupled with hydrogen production at the specified current density; during discharge, under illumination, ethylene glycol oxidation occurs at the negative electrode, such as... Figure 11 As shown, at 0.8 mA cm -2 At a discharge current density of [value missing], the battery can discharge at a voltage of ~1.3 V, with a capacity of 3.62 Ah L. -1 During this discharge process, the battery's state of charge (SOC) gradually decreases, while the battery continues to selectively oxidize ethylene glycol to yield glycolic acid and formic acid. The overall Faraday efficiency for the liquid products still reaches 91.2%, with a formic acid yield of 3.84 μmol / cm³. -2 h -1 The yield of glycolic acid was 1.04 μmol / cm³. -2 h -1 .

[0063] Application Example 2

[0064] A photoelectric open-circuit flow battery reactor:

[0065] The photoanode was used as the positive electrode for charging, and the photoanode was a TiO2 catalyst supported on FTO conductive glass. The positive electrode electrolyte contained 0.2 M VO2. 2+The electrolyte is 2 M H2SO4; the negative electrode is a graphite felt loaded with Pt nanoparticles, which together with the 2 M H2SO4 electrolyte forms the negative electrode; a Nafion 117 membrane is placed between the positive and negative electrodes.

[0066] The photoanode was used as the negative electrode for discharge, and the photoanode was a TiO2 catalyst supported on FTO. The negative electrode electrolyte was a 1 M KOH electrolyte containing 0.1 M glycerol organic substrate. The positive electrode for discharge was an inert graphite felt electrode containing 0.2 M VO2. + A 2 M H2SO4 electrolyte forms the positive electrode; a Nafion 117 membrane is placed between the positive and negative electrodes.

[0067] At an irradiation power density of 100 mW / cm² 2 Under a light source, the photoelectric open-circuit flow battery at 0.8 mA cm⁻¹ -2 Constant current charging is performed at the bottom, and the positive electrode will release the VO in the positive electrode electrolyte. 2+ Oxidized to VO2 + During discharge, under illumination, glycerol oxidation occurs at the negative electrode, as shown in the discharge curve. Figure 12 As shown, at 0.8 mA cm -2 At a discharge current density of [value missing], the battery can discharge at a voltage of ~1.4 V, with a capacity of 3.51 Ah L. -1 During this discharge process, the battery's state of charge (SOC) gradually decreases, while the battery continuously performs selective oxidation of glycerol, selectively converting glycerol into high-value-added products such as glycolic acid, formic acid, and glyceric acid. The overall Faraday efficiency of the liquid products can still reach 93.6%.

[0068] Application Example 3

[0069] A photoelectric open-circuit flow battery reactor:

[0070] The photoanode was used as the positive electrode for charging, and the photoanode was a TiO2 catalyst supported on FTO conductive glass. The positive electrode electrolyte contained 0.2 M VO2. 2+ The electrolyte is 2 M H2SO4; the negative electrode is a graphite felt loaded with Pt nanoparticles, which together with the 2 M H2SO4 electrolyte forms the negative electrode; a Nafion 117 membrane is placed between the positive and negative electrodes.

[0071] The photoanode was used as the negative electrode for discharge, and the photoanode was a TiO2 catalyst supported on FTO. The negative electrode electrolyte was a 1 M KOH electrolyte containing 0.1 M benzyl alcohol as the organic substrate. The positive electrode for discharge was an inert graphite felt electrode containing 0.2 M VO2.+ A 2 M H2SO4 electrolyte forms the positive electrode; a Nafion 117 membrane is placed between the positive and negative electrodes.

[0072] At an irradiation power density of 100 mW / cm² 2 Under a light source, the photoelectric open-circuit flow battery at 0.8 mA cm⁻¹ -2 Constant current charging is performed at the bottom, and the positive electrode will release the VO in the positive electrode electrolyte. 2+ Oxidized to VO2 + HER occurs at the negative electrode; during discharge, under illumination, benzyl alcohol is oxidized at the negative electrode, as shown in the discharge curve. Figure 13 As shown, at 0.8 mA cm -2 At a discharge current density of [value missing], the battery can discharge at a voltage of ~1.5 V, with a capacity of 3.39 Ah L. -1 During this discharge process, the battery's state of charge (SOC) gradually decreases, while the battery continuously and selectively oxidizes benzyl alcohol, converting it into the high-value-added product benzaldehyde. The overall Faraday efficiency reaches 87.2%, with a benzaldehyde yield of 2.24 μmol / cm³. -2 h -1 .

[0073] This invention couples photoelectrocatalysis (PEC) selective oxidation of organic matter with flow battery energy storage, thereby achieving dual-path storage of solar energy. It converts solar energy into the chemical energy of organic oxidation products through the photoelectrocatalysis process, and stores electrical energy based on the flow battery architecture. This provides a feasible solution to alleviate the inherent spatiotemporal discontinuity of solar energy and further promotes the development of photoelectrocatalysis systems in new application scenarios.

[0074] It should be noted that, unless otherwise specified, the embodiments and features described in these embodiments can be combined with each other.

[0075] In the description of this utility model, it should be understood that the terms "center," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicating orientation or positional relationships based on the orientation or positional relationships shown in the accompanying drawings, are only for the convenience of describing this utility model and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this utility model. Furthermore, the terms "first," "second," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, features defined with "first," "second," etc., may explicitly or implicitly include one or more of that feature. In the description of this utility model, unless otherwise stated, "a plurality of" means two or more.

[0076] In the description of this utility model, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "joining" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this utility model based on the specific circumstances.

[0077] The applicant declares that the above description is only a specific embodiment of the present utility model, but the protection scope of the present utility model is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present utility model fall within the protection and disclosure scope of the present utility model.

Claims

1. A photoelectrochemical open-circuit flow battery reactor, characterized by: It includes two mirror-symmetrical end plates (1) and an anode (3) and a cathode (6) disposed between the two end plates (1). An ion exchange membrane (5) is disposed between the anode (3) and the cathode (6). A sealing plate (4) is disposed between the anode (3) and the ion exchange membrane (5) and between the cathode (6) and the ion exchange membrane (5). A gasket (2) is disposed between the end plate (1) on the anode side and the anode (3) and between the end plate (1) on the cathode side and the cathode (6). The two end plates (1) and the two gaskets (2) are fastened together by bolts, and the anode (3), the sealing plate (4), the ion exchange membrane (5) and the cathode (6) are pressed between the two gaskets (2).

2. The photoelectric open-circuit flow battery reactor according to claim 1, characterized in that: The end plate (1) is a plate-shaped structure. Multiple end plate fixing holes (11), multiple end plate positioning holes (12), and electrolyte inlet (14) and electrolyte outlet (15) arranged diagonally are formed on the end plate (1). The horizontal position of the electrolyte inlet (14) is lower than the horizontal position of the electrolyte outlet (15). Multiple end plate fixing holes (11) are arranged around the end plate (1). The end plate positioning holes (12) are arranged inside the end plate fixing holes (11). An end plate window (13) is formed in the middle of the end plate (1) on the anode side.

3. The photoelectrochemical open-circuit flow battery reactor of claim 1, wherein: The gasket (2) has a plate-like structure. Multiple gasket fixing holes (21), multiple gasket positioning holes (22), and gasket liquid inlet (23) and gasket liquid outlet (24) arranged diagonally are formed on the gasket (2). The gasket positioning holes (22) are arranged one-to-one with the end plate positioning holes (12). The gasket liquid inlet (23) is arranged correspondingly with the electrolyte liquid inlet (14) and is interconnected. The gasket liquid outlet (24) is arranged correspondingly with the electrolyte liquid outlet (15) and is interconnected. The number of gasket fixing holes (21) is not greater than the number of end plate fixing holes (11), and the position of the gasket fixing holes (21) corresponds to the position of the end plate fixing holes (11). A gasket window (25) is formed in the middle of the gasket (2) on the anode side. The gasket window (25) has the same size as the end plate window (13) and is arranged in a corresponding position.

4. The photoelectrochemical open-circuit flow battery reactor of claim 1, wherein: The anode (3) is a plate-shaped structure, which includes a photoanode (31), an anode current collector (33) and an anode flow channel plate (34). A sealing gasket (32) is provided between the photoanode (31) and the anode flow channel plate (34). The anode flow channel plate (34) is located close to the ion exchange membrane (5). One end of the anode current collector (33) is in contact with the photoanode (31), and the other end is higher than the top of the end plate (1).

5. The photoelectrochemical open-circuit flow battery reactor of claim 4, wherein: The photoanode (31) has a plate-like structure with a connecting protrusion at its upper end; the photoanode (31) is composed of a catalyst layer supported on a conductive substrate, and the catalyst layer is positioned close to the anode flow channel plate (34).

6. The photoelectric open-circuit flow battery reactor according to claim 4, characterized in that: The anode current collector (33) is a strip structure, in which grooves are formed on both sides of the lower section, and the grooves divide the anode current collector (33) into a power connection section, an embedding section and a connecting section.

7. The photoelectrochemical open-circuit flow battery reactor of claim 4, wherein: The anode flow channel plate (34) has a plate-like structure, and an anode electrolyte tank (349) is formed in the middle of the anode flow channel plate (34). The diagonal of the anode electrolyte tank (349) forms an anode flow channel plate inlet (344) and an anode flow channel plate outlet (345), both of which are connected to the anode electrolyte tank (349). The anode flow channel plate inlet (344) and the gasket inlet (23) are correspondingly arranged and connected to each other. The anode flow channel plate outlet (345) and the gasket outlet (24) are correspondingly arranged and connected to each other. An anode flow channel plate sealing gasket groove (346) is formed around the anode electrolyte tank (349), and the sealing gasket (32) is placed in the center of the groove. The anode flow channel plate sealing gasket groove (346) is located inside; a stepped groove is formed above the anode electrolyte tank (349), which is composed of a small-diameter anode flow channel plate manifold groove (348) and a large-diameter anode flow channel plate light anode groove (347); the connecting protrusion of the light anode (31) is embedded in the light anode groove (347) of the anode flow channel plate; the embedded section of the anode manifold (33) is embedded in the anode flow channel plate manifold groove (348), and its connecting section is embedded in the light anode groove (347) of the anode flow channel plate and contacts the connecting protrusion of the light anode (31); multiple anode flow channel plate positioning holes (341) are formed on both sides of the anode electrolyte tank (349), and the anode flow channel plate positioning holes (341) are set one-to-one with the gasket positioning holes (22).

8. The photoelectrochemical open-circuit flow battery reactor of claim 1, wherein: The sealing plate (4) is a plate-shaped structure. A catalyst groove (42) is formed in the middle of the sealing plate (4), and multiple sealing plate positioning holes (41) are formed around the catalyst groove (42). The catalyst groove (42) is a through groove, and the sealing plate positioning holes (41) and the end plate positioning holes (12) are set one-to-one.

9. The photoelectrochemical open-circuit flow battery reactor of claim 1, wherein: The cathode (6) includes a cathode catalyst (61), a cathode flow channel plate (62) and a cathode current collector (63) arranged in sequence; the cathode catalyst (61) is arranged close to the ion exchange membrane (5).

10. The photoelectric open-circuit flow battery reactor according to claim 9, characterized in that: The cathode flow channel plate (62) has a plate-like structure, in which a flow channel field (624) is formed in the middle. The diagonals of the flow channel field (624) form the cathode electrolyte inlet (622) and the cathode electrolyte outlet (623), respectively. The cathode electrolyte inlet (622) and the cathode electrolyte outlet (623) are connected to the flow channel field (624) through connecting channels. The flow channel field (624) is a serpentine flow channel field formed by the serpentine coiling of the flow channel. The cathode catalyst (61) is in contact with the flow channel field (624). Multiple cathode flow channel plate positioning holes (621) are formed on both sides of the flow channel field (624). The cathode flow channel plate positioning holes (621) are set one-to-one with the sealing plate positioning holes (41). The structure of the cathode current collector (63) is the same as that of the gasket (2) on the cathode side. The length of the cathode current collector (63) is greater than that of the gasket (2) on the cathode side.

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