Protective film, underground space electrolyte reservoir and preparation method thereof, leak detection system and leak detection method thereof

Abstract

The application relates to the technical field of leak detection, and provides a protective film, an underground space electrolyte storage and a preparation method thereof, a leak detection system and a leak detection method thereof, which are arranged on the inner wall surface of an electrolyte storage container for storing electrolyte, contain an electrically conductive layer and an anticorrosion layer combined with each other, and the anticorrosion layer is in contact with the electrolyte. The anticorrosion layer contained in the protective film can prevent the electrolyte from corroding the inner wall surface of the electrolyte storage container, and the electrically conductive layer contained in the protective film can be used as part of a leak detection system or a leak detection device, so that the leak detection work on the electrolyte can be completed.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of leak detection, and particularly relates to a protective film, an underground space electrolyte storage device, a preparation method thereof, a leak detection system and a leak detection method thereof. BACKGROUND

[0002] High proportion of renewable energy puts higher requirements on the flexible adjustment capability of the power system, and a large number of energy storage systems need to be matched to ensure the stability of the power grid.

[0003] As a new generation of energy storage technology, the flow battery and the electric fuel energy storage system have been widely concerned due to good scalability, high safety and long service life. The electrolyte of the flow battery and the electric fuel energy storage system is mostly a liquid solution containing ions. Limited by the solubility of active substances, the energy density of the electrolyte is generally low, and a large space and land cost are required for storage on the ground. In addition, the electrolyte is rich in acid, alkali or heavy metal ions. Once the liquid storage tank leaks, not only the metal protection cavity of the system (such as the electrolyte tank support layer, the pipeline support and the outer shell of the stack container) will be corroded, but also the surrounding environment will be polluted. In addition, the temperature of the ground environment changes greatly in four seasons and day and night. In order to prevent the precipitation or denaturation decomposition of active substances due to too high or too low temperature, the electrolyte needs to be maintained at a certain temperature. When the temperature is high, the liquid storage tank needs to be cooled (depending on the cooling system), and when the temperature is low, the liquid storage tank needs to be heated (depending on the heating system), which consumes a lot of energy. The use of underground space such as salt caverns and caves to store liquid flow and electrolyte of the electric fuel energy storage system can alleviate the pressure of land space on the ground, prevent the influence of electrolyte leakage on the surrounding environment, and reduce the energy consumption of electrolyte temperature control, which has great development prospects.

[0004] Currently, there are the following problems in directly storing the electrolyte of the flow battery and the electric fuel system in the underground space: first, the rock wall of the underground space is rich in iron oxide, aluminum oxide, silicon dioxide, clay, carbonate or silicate (such as the main chemical composition of marble is calcium carbonate, the main component of mica is aluminum silicate, and the main component of basalt is silicon dioxide and silicate), which will react with acidic or alkaline electrolyte when directly contacted, on the one hand, the rock wall will be corroded, and on the other hand, the concentration of acid or alkali in the electrolyte will be reduced, causing irreversible performance degradation of the flow battery and the electric fuel system. Secondly, the heavy metal ions in the electrolyte will dissolve in the underground water after penetrating into the rock wall, causing damage to the ecological environment. SUMMARY

[0005] The application aims to provide a protective film, an underground space electrolyte storage device, a preparation method thereof, a leak detection system and a leak detection method thereof, and aims to solve the problems that the electrolyte storage container in the prior art is corroded by the electrolyte, and the power supply performance of the flow battery and the electric fuel system is irreversibly degraded.

[0006] To achieve the above-mentioned application purposes, the technical solutions adopted by the present application are as follows:

[0007] The first aspect of the present application provides a protective film arranged on the inner wall surface of an electrolyte storage container for storing electrolyte, which comprises an electrically conductive layer and an anticorrosion layer combined with each other, and the anticorrosion layer is in contact with the electrolyte.

[0008] The anticorrosion layer contained in the protective film provided by the present application can prevent the electrolyte from corroding the inner wall surface of the electrolyte storage container, and the electrically conductive layer contained in the protective film can be part of a leak detection system or leak detection device, thereby completing the leak detection work of the electrolyte.

[0009] The second aspect of the present application provides an underground space electrolyte storage container, and at least one region of the inner wall surface of the underground space electrolyte storage container is provided with the protective film of the present application.

[0010] The underground space electrolyte storage container provided by the present application can collect the leaked electrolyte through the drainage system directly into the ground space when the ground electrode or pipeline leaks, which can prevent the leaked electrolyte from polluting the environment on the one hand, and can avoid the capacity reduction caused by the waste of electrolyte on the other hand.

[0011] The third aspect of the present application provides a preparation method of an underground space electrolyte storage container, the depth of the required drilling is calculated according to the capacity of the underground space electrolyte storage container, the energy density of the electrolyte, the space idle rate, and the diameter of the drill bit, the ground is drilled to obtain an underground cavity.

[0012] The required drilling depth can be calculated according to the capacity of the underground space electrolyte storage container, and the formula is as follows:

[0013] (1)

[0014] Wherein, E is the energy of the required stored electrolyte, and the unit is watt-hour;

[0015] n is the number of liquid storage tanks;

[0016] e is the energy density of the electrolyte, and the unit is watt-hour / cubic meter;

[0017] η is the space idle rate of the liquid storage;

[0018] U is the utilization rate of the electrolyte;

[0019] d is the diameter of the drill bit, and the unit is meter;

[0020] The underground space electrolyte storage container is formed by arranging the protective film of the present application in at least one region of the inner wall surface of the underground cavity.

[0021] The application discloses a preparation method of an underground space electrolyte storage container.

[0022] The fourth aspect of the application provides a leak detection system, which comprises the underground space electrolyte storage container, the electrolyte, the detection device, the first conductor, the second conductor, the third conductor and the loop detection conductor.

[0023] At least one region of the inner wall of the underground space electrolyte storage container is provided with the protective film, and the end of the conductive layer of the protective film at or near the top of the electrolyte storage container is set as an A part, and the end of the conductive layer of the protective film at or near the bottom of the electrolyte storage container is set as a B part.

[0024] The electrolyte is stored in the electrolyte storage container and directly contacts the corrosion-resistant layer.

[0025] One end of the loop detection conductor is set as a D part and is inserted below the liquid level of the electrolyte, and the other end is set as an E part and is arranged above the liquid level of the electrolyte.

[0026] The first conductor is connected with the A part, the second conductor is connected with the B part, the third conductor is connected with the E part, and the detection device is connected with the first conductor, the second conductor and the third conductor respectively, so as to detect the resistance between the A part and the B part, the resistance between the A part and the E part and the resistance between the B part and the E part.

[0027] The leak detection system provided by the embodiment of the application can detect the resistance between the A part and the B part, the resistance between the A part and the E part and the resistance between the B part and the E part through the detection device.

[0028] The fifth aspect of the embodiment of the application provides a leak detection method, which comprises the leak detection method of the leak detection system of the embodiment of the application, and comprises the following steps.

[0029] The resistance between the A part and the B part is measured by the detection device, and the measurement value is y1.

[0030] The resistance value between the A part and the E part is measured by the detection device, and the measurement value is y2, wherein y2 comprises R1+R e +R t , R1 is the electronic resistance from the A part to the C part, R e is the ionic resistance from the C part to the D part, and R t is the electronic resistance from the E part to the B part, wherein the C part is the position where the corrosion-resistant layer is broken.

[0031] The resistance between the B part and the E part is measured by the detection device, and the measured value is y3, wherein y3 includes R2+R e +R t R2 is the electronic resistance from the B part to the C part;

[0032] The height of the rupture position is calculated according to the following formula:

[0033] R1+R2=y1(1)

[0034] R1+R e +R t =y2(2)

[0035] R2+R e +R t =y3(3)

[0036] Solving the equations (1), (2) and (3), the value of R1 is (y1+y2-y3) / 2, and the value of R2 is (y1-y2+y3) / 2;

[0037] The positions of the A part, the B part and the C part satisfy the following relationship:

[0038] L1+L2=L(4)

[0039] L1 / L2=R1 / R2(5)

[0040] Combining the values of R1 and R2 and the equations (4) and (5), L1=L×(y1+y2-y3) / 2y1, L2=L×(y1-y2+y3) / 2y1 are obtained, wherein L is the distance from the A part to the B part, L1 is the vertical distance from the C part to the A part, L2 is the vertical distance from the C part to the B part.

[0041] The leak detection method provided in the application can calculate the height of the rupture position of the conductive layer in the protective film by detecting the resistance between the A part and the B part, the resistance between the A part and the E part, and the data of the resistance between the B part and the E part. BRIEF DESCRIPTION OF DRAWINGS

[0042] Figure 1 A structural diagram of a protective film provided in an embodiment of the application;

[0043] Figure 2 A structural diagram of another protective film provided in an embodiment of the application;

[0044] Figure 3 A leak detection system provided in an embodiment of the application;

[0045] Figure 4 Another leak detection system is provided for embodiments of the present application.

[0046] Reference signs

[0047] 10 - detection device; 11 - first conductor; 12 - second conductor; 13 - third conductor; 14 - first switch, 15 - second switch, 16 - third switch; 3 - anticorrosion layer; 4 - conductive layer; 5 - loop detection conductor; 6 - isolation layer; 7 - electrolyte storage container. DETAILED DESCRIPTION

[0048] In order to make the technical problems to be solved, technical solutions and beneficial effects of the present application clearer, the present application will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and not intended to limit the present application.

[0049] In the present application, the term "and / or" describes the association relationship of the associated objects, which means that there can be three kinds of relationships, for example, A and / or B can mean that A exists alone, A and B exist together, and B exists alone. Wherein A and B can be singular or plural. The character " / " generally represents an "or" relationship between the associated objects before and after it.

[0050] In the present application, "at least one" means one or more, and "multiple" means two or more. "At least one" or similar expressions refer to any combination of these items, including any combination of single item or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can mean a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple.

[0051] It should be understood that in various embodiments of the present application, the size of the sequence number of the above processes does not mean the order of execution, and part or all of the steps can be executed in parallel or in sequence. The execution order of each process should be determined according to its function and inherent logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0052] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of the present application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0053] The weight of the related components mentioned in the embodiment specification of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of each component. Therefore, as long as the content of the related components in the embodiment specification of the present application is proportionally enlarged or reduced, it is within the scope disclosed in the embodiment specification of the present application. Specifically, the mass mentioned in the embodiment specification of the present application can be µg, mg, g, kg, and other mass units commonly known in the chemical industry.

[0054] The terms "first", "second" are only for descriptive purposes and are used to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. For example, without departing from the scope of the present application, the first XX can also be referred to as the second XX, and similarly, the second XX can also be referred to as the first XX. Therefore, the features defined with "first", "second" can explicitly or implicitly include one or more of the features.

[0055] The first aspect of the embodiment of the present application provides a protective film arranged on the inner wall surface of an electrolyte storage container for storing electrolyte, which comprises an electrically conductive layer and an anticorrosion layer combined with each other, and the anticorrosion layer is in contact with the electrolyte.

[0056] The protective film provided by the embodiment of the present application can isolate the inner wall surface of the electrolyte storage container and the electrolyte through the cooperation of the electrically conductive layer and the anticorrosion layer, prevent the electrolyte from corroding the inner wall surface of the electrolyte storage container, and when the anticorrosion layer is broken, the electrically conductive layer can be part of a leak detection system or leak detection device to complete the leak detection of the electrolyte. The electrolyte storage container includes the wall surface of the underground space, the wall surface of the electrolyte container, and the wall surface of the electrolyte pool. In addition, the physical volume of the underground space is in the range of 10 3 ~10 6 m 3 The geothermal temperature is in the range of 25~75℃.

[0057] In some embodiments, the anticorrosion layer includes one or a composite layer formed by two of the anticorrosive coating layer or the resin layer, and the anticorrosion layer can resist the corrosion of the electrolyte to the electrolyte storage container.

[0058] In some embodiments, the material forming the resin layer includes at least one of polyvinyl chloride, polypropylene, or polytetrafluoroethylene, which is inexpensive and helps to save costs.

[0059] In some embodiments, the coating forming the anticorrosion coating layer includes any one or a composite film layer formed by two of the epoxy resin film layer or the phenolic resin film layer, and the anticorrosion coating layer can isolate the inner wall surface of the electrolyte storage container and the electrolyte, thereby preventing the electrolyte from corroding the inner wall surface of the electrolyte storage container.

[0060] Further, the coating for forming the epoxy resin film layer includes a component A and a component B, wherein

[0061] The component A includes:

[0062] Epoxy resin 30-50 parts

[0063] Amine curing agent 10-30 parts

[0064] The component B includes:

[0065] Polysiloxane leveling agent 0.1-1 parts

[0066] Polysiloxane foaming agent 0.01-0.1 parts

[0067] Dispersant 0.1-1.5 parts

[0068] Toughening agent 2-10 parts

[0069] Talc 3-8 parts

[0070] Zinc sulfate 3-11 parts

[0071] Aluminum tripolyphosphate 3-8 parts

[0072] Mica powder 3-8 parts

[0073] Baryte powder 6-15 parts

[0074] Titanium dioxide 3-8 parts

[0075] The epoxy resin film layer is arranged on the inner wall surface of the electrolyte storage container to insulate the inner wall surface of the electrolyte storage container, so that the electrolyte corrosion of the inner wall surface of the electrolyte storage container is prevented. The one-time film thickness of the epoxy resin film layer is about 600 μm, which has no pollution to water, has very good adhesion to smooth rock wall, and has very good impact resistance to flowing electrolyte. The epoxy resin film layer has very good resistance to solutions with mass fraction of less than 60% of sulfuric acid, 31% of hydrochloric acid and 50% of sodium hydroxide.

[0076] In some embodiments, the toughening agent in the component B is one or a mixture of several of butadiene-acrylonitrile rubber, polysulfide rubber and epoxy-terminated polyurethane.

[0077] Further, the preparation method of the coating of the epoxy resin film layer includes the following steps: adding a diluent to the epoxy resin, and performing first mixing treatment by a high-speed rotary stirrer; then adding a toughening agent to the high-speed rotary stirrer to perform second mixing treatment; finally adding various additives to the high-speed rotary stirrer to perform third mixing treatment; and finally grinding the uniformly dispersed materials to obtain the required coating slurry. In the stirring process, the temperature should not exceed 60°C to prevent the properties of the materials from changing.

[0078] Further, the coating for forming the phenolic resin film layer includes a C component and a D component, wherein,

[0079] The C component includes:

[0080] Cardanol-modified phenolic resin 40-52 parts

[0081] Alkyd resin 20-23 parts

[0082] Titanium white 10-16 parts

[0083] The D component includes:

[0084] Rosin water-soluble solvent oil 7.3 parts

[0085] Wetting agent 0.8 parts

[0086] Anti-settling dispersant 0.5 parts

[0087] Defoaming agent 0.2 parts

[0088] Oxidation polymerization type drier 0.15 parts

[0089] Anti-skinning agent 0.05 parts.

[0090] The phenolic resin film layer is arranged on the inner wall surface of the electrolyte storage container, and the inner wall surface of the electrolyte storage container is insulated, so that the electrolyte corrosion of the inner wall surface of the electrolyte storage container is prevented. The biggest advantage of the phenolic resin film layer in the embodiment is environmental protection, acid resistance, high temperature resistance, and wear resistance. Since the oxidation polymerization type drier is used to replace the metal driers such as cobalt, manganese, and lead, the final film layer does not contain substances that pollute the rock layer and the nearby underground water. The highest temperature resistance of the phenolic resin film layer can reach 150°C or above, and the film layer has very good durability in salt water, inorganic acid (sulfuric acid and hydrochloric acid), and oxidizing substances (valuable vanadium ions and iron ions in electrolyte). In addition, the phenolic resin film layer of the embodiment is easy to construct and has a high cost performance.

[0091] Further, the coating for forming the phenolic resin film layer includes a C component and a D component, wherein,

[0092] The cardanol-modified phenolic resin is obtained by alcoholization and esterification of cashew nut shell liquid, rosin water-soluble solvent oil is added to the modified phenolic resin and alkyd resin, and a high-speed rotary stirrer is used for first mixing treatment. Then, titanium white is added to the high-speed rotary stirrer for second mixing treatment. Finally, wetting agent, anti-settling dispersant, and defoaming agent are sequentially added to the high-speed rotary stirrer, and the solution is dried by a drier and a skinning agent.

[0093] In some embodiments, the conductive layer includes a conductive coating, a metal mesh, a metal foam layer, or a composite layer formed by one or two layers of metal fibers.

[0094] In some embodiments, the thickness of the conductive layer is 400-800 μm.

[0095] In some embodiments, the metal in the metal mesh, metal foam layer, metal fiber layer is the same or different and includes at least one of copper, stainless steel, tungsten, titanium, nickel-chromium, molybdenum, silver. The metal mesh structure plays a certain mechanical supporting role on the resin layer on the one hand, and can electrolyte, loop detection conductor form a monitoring loop on the other hand.

[0096] In some embodiments, the paint for forming the conductive film layer includes a curing agent, a conductive agent, a corrosion inhibitor, and other auxiliary agents.

[0097] In some embodiments, the conductive agent includes one of a conductive polymer material, a conductive carbon material, and a conductive metal.

[0098] Further, the conductive agent includes a conductive powdery substance, wherein the conductive polymer material includes at least one of polypyrrole powder or polyaniline powder, the conductive carbon material includes at least one of carbon powder, graphene, and carbon nanotube, and the conductive metal includes at least one of copper powder, zinc powder, and iron powder.

[0099] In some embodiments, the other auxiliary agents include a corrosion inhibitor, an active diluent, a curing agent, a curing accelerator, a defoaming agent, and a plasticizer.

[0100] Further, the paint for forming the conductive film layer includes the following components:

[0101] Conductive powder 1-40 parts

[0102] Corrosion inhibitor 10-65 parts;

[0103] Active diluent 2-25 parts;

[0104] Curing agent 4-27 parts;

[0105] Curing accelerator 0.25-4 parts;

[0106] Defoaming agent 0.1-1 part;

[0107] Plasticizer 2-15 parts.

[0108] The active diluent is propylene carbonate, the curing agent includes diaminodiphenyl methane, the curing accelerator includes phenol, the defoaming agent includes methyl silicone oil or dimethyl silicone oil, and the plasticizer includes at least one of dibutyl phthalate, dioctyl phthalate, triphenyl phosphate, or trimethylphenyl phosphate.

[0109] The coating for forming the conductive film layer can form a film layer with conductive function on the inner wall surface of the electrolyte storage container, and the film layer can be used as part of the electrolyte leak detection device or electrolyte leak detection system to detect the leakage of electrolyte.

[0110] Further, the preparation method of the coating for forming the conductive film layer comprises the following steps:

[0111] The conductive coating preparation method comprises the following steps: taking several conductive powders, adding a curing agent under mechanical stirring, heating to 50-80℃, rapid stirring for 2-5h, and then reducing to room temperature; adding an active diluent, a defoaming agent, and a plasticizer into the epoxy resin and mixing uniformly; adding a curing accelerator; and then adding the prepared mixed curing agent into the conductive powder to obtain a conductive low-viscosity anticorrosive coating.

[0112] In some embodiments, the isolation layer comprises a bonding film layer or a foam layer, which isolates the inner wall surface of the electrolyte storage container and the conductive layer.

[0113] In some embodiments, the material for forming the foam layer comprises one of a polyurethane foaming material, a polystyrene foaming material, a polyvinyl chloride foaming material, or a polyethylene foaming material, which can prevent the soil from eroding the metal mesh shell and can protect the plastic shell from the impact of electrolyte flow during the operation of the battery.

[0114] In some embodiments, the isolation layer is further included and is stacked between the conductive layer and the inner wall surface of the electrolyte storage container supporting the protective film.

[0115] In some embodiments, the isolation layer comprises a bonding film layer or a foam layer. The bonding film layer can improve the connectivity between the protective film and the inner wall surface of the electrolyte storage container and isolate the inner wall surface of the electrolyte storage container and the conductive layer. The foam layer mainly has three functions: one is to prevent the soil from eroding the metal mesh shell, the other is to protect the plastic shell from the impact of electrolyte flow during the operation of the battery, and the third is to prevent the direct contact between the soil and the electrolyte when the plastic shell is broken.

[0116] In some embodiments, the coating for forming the bonding film layer comprises a silicon-titanium oxide-based gel, which can increase the resistance of the bonding film layer to electrolyte corrosion.

[0117] Further, the coating for forming the bonding film layer comprises the following components mixed in the following proportions by weight:

[0118] Polydimethylsiloxane 10-15 parts

[0119] Ethyl orthosilicate, butyl phthalate and propyl trimethoxy 85-90 parts.

[0120] In the application, the adhesive film formed by the coating has good resistance to hydrochloric acid and strong alkali corrosion in the electrolyte.

[0121] Further, the coating preparation method of the adhesive film layer comprises the following steps: mixing ethyl orthosilicate with anhydrous ethanol and acetic acid, adding propyl trimethoxy silane after heating, adding polydimethylsiloxane dissolved by ethanol, and finally adding acetylacetone, N, N-dimethylformamide and butyl phthalate in sequence to form a silicon-titanium oxide gel. The application has very good adhesion to rock walls and good resistance to hydrochloric acid and strong alkali corrosion in the electrolyte.

[0122] The second aspect of the application provides an underground space electrolyte storage container, at least one region of the inner wall surface of the underground space electrolyte storage container is provided with the protective film. The underground space includes salt caves, rock caves and artificial underground caves.

[0123] The underground space electrolyte storage container provided by the application can collect the leaked electrolyte through the drainage system and directly into the ground space when the ground electrode or pipeline leaks, which can prevent the leaked electrolyte from polluting the environment and avoid the capacity reduction caused by the waste of electrolyte.

[0124] In addition, the working temperature range of the flow battery is narrow. The underground space is stable, and the soil and rock layer has good heat conduction. The heat generated during the operation of the flow battery can be discharged through the soil in time, reducing the dependence of the flow battery on the cooling system. In addition, the underground space has good insulation effect in winter, and is less affected by the ground climate, which can reduce the dependence of the flow battery system on the heating system. For the storage of electrolyte, the heat management of the battery has a very positive effect.

[0125] The third aspect of the application provides a preparation method of an underground space electrolyte storage container. The required drilling depth is calculated according to the capacity of the underground space electrolyte storage container, the energy density of the electrolyte, the space idle rate and the diameter of the drill bit, the ground is drilled to obtain an underground cave.

[0126] The required drilling depth can be calculated according to the capacity of the underground space electrolyte storage container, and the formula is as follows:

[0127] (1)

[0128] Wherein, E is the energy of the electrolyte to be stored, and the unit is watt-hour;

[0129] n is the number of liquid storage tanks;

[0130] e is the energy density of the electrolyte, in units of watt-hour per cubic meter;

[0131] η is the empty space of the electrolyte storage space;

[0132] U is the utilization rate of the electrolyte;

[0133] d is the diameter of the drill bit, in meters;

[0134] The protective film is arranged on at least one region of the inner wall surface of the underground cavity to form the underground space electrolyte storage container.

[0135] The preparation method of the underground space electrolyte storage container according to the embodiment of the application can accurately calculate the drilling depth according to the energy storage capacity, drill bit diameter, electrolyte concentration and other parameters, greatly save the ground space, and reduce the land occupation cost of the electrolyte storage of the liquid flow battery and the electric fuel system.

[0136] The fourth aspect of the embodiment of the application provides a leak detection system, which comprises the underground space electrolyte storage container, the electrolyte, the detection device, the first conductor, the second conductor, the third conductor and the loop detection conductor of the above-mentioned embodiment of the application.

[0137] Specifically, as shown in Figures 1 to 4 The end of the conductive layer 4 of the protective film at or near the top of the electrolyte storage container 7 is set as the A part, and the end of the conductive layer 4 of the protective film at or near the bottom of the electrolyte storage container 7 is set as the B part.

[0138] One end of the loop detection conductor 5 is set as the D part and is inserted below the liquid level of the electrolyte, and the other end is set as the E part and is arranged above the liquid level of the electrolyte.

[0139] The electrolyte is stored in the electrolyte storage container 7.

[0140] The first conductor 11 of the detection device 10 is connected with the A part, the second conductor 12 is connected with the B part, and the third conductor 13 is connected with the E part. The detection device 10 is connected with the first conductor 11, the second conductor 12 and the third conductor 13 respectively, and is used for detecting the resistance between the A part and the B part, the resistance between the A part and the E part, and the resistance between the B part and the E part respectively.

[0141] In the leak detection system, when the anticorrosion layer 3 is intact, the conductive layer 4 is isolated from the electrolyte, and there is no contact between them. At this time, the loop detection conductor 5 cannot form a loop with the conductive layer 4, and is in an open circuit state. Therefore, the voltage and resistance between the conductive layer and the loop detection conductor 5 tend to infinity. When the anticorrosion layer 3 is broken, the conductive layer 4 and the electrolyte are in contact with each other, and a potential difference is generated. Then, a voltage (usually less than 0.5V) and a measurable resistance are generated between the conductive layer 4 and the loop detection conductor 5.

[0142] Further, the detection device 10 further comprises a first switch 14, a second switch 15 and a third switch 16. The first switch 14 is used to control the closing of the first conductor 11, the second switch 15 is used to control the closing of the second conductor 12, and the third switch 16 is used to control the closing of the third conductor 13.

[0143] In the leak detection system, when the first switch 14 and the second switch 15 are closed, and the third switch 16 is not closed, the detection device 10, the A part, the first conductor 11, the second conductor 12 and the B part form a first loop, and the resistance between the A part and the B part is detected.

[0144] In the leak detection system, when the first switch 14 and the third switch 16 are closed, and the second switch 15 is not closed, the detection device 10, the electrolyte, the A part, the first conductor 11, the third conductor 13, the C part and the E part form a second loop. The detection device 10 can detect the resistance between the A part and the E part.

[0145] In the leak detection system, when the second switch 15 and the third switch 16 are closed, and the first switch is not closed, the detection device 10, the electrolyte, the B part, the second conductor 12, the third conductor 13 and the E part form a third loop. The detection device 10 can detect the resistance between the B part and the E part.

[0146] The leak detection system provided by the embodiment of the application can calculate the height of the broken position of the conductive layer in the protective film by detecting the resistance between the A part and the B part, the resistance between the A part and the E part, and the resistance between the B part and the E part.

[0147] Further, the leak detection system further comprises an alarm device (not labeled in the figure), which can monitor whether the electrolyte leaks in real time.

[0148] Further, the leak detection system further comprises a display device (not labeled in the figure), which displays the height information of the broken position to the staff, so that the staff can adjust the height of the electrolyte according to the height of the broken position.

[0149] In some embodiments, the loop detection conductor 5 comprises one of a graphite rod, a graphite composite, a copper rod, a 316 stainless steel rod and other metal rods that can stably exist in the electrolyte, wherein the loop detection conductor 5 comprises an electronic good conductor that can stably exist in the electrolyte.

[0150] Further, for the acidic electrolyte, the loop detection conductor 5 is selected from the graphite rod and the graphite composite, and for the alkaline and neutral electrolyte, the loop detection conductor 5 is selected from the metal rod and the 316 stainless steel rod, wherein the leak detection system places the loop detection conductor 5 in the space containing the electrolyte during use, and the bottom of the loop detection conductor 5 is arranged below the liquid level of the electrolyte.

[0151] The fifth aspect of the embodiments of the present application provides a leak detection method, comprising the leak detection method performed by the leak detection system of the embodiments of the present application, comprising the following steps:

[0152] Step S1, measuring the resistance between the A part and the B part by the detection device 10, and the measurement value is y1;

[0153] Step S2, measuring the resistance value between the A part and the E part by the detection device, and the measurement value is y2, wherein y2 comprises R1+R e +R t , R1 is the electronic resistance from the A part to the C part, R e is the ionic resistance from the C part to the D part, and R t is the electronic resistance from the E part to the B part, wherein the C part is the position where the corrosion-resistant layer 3 is broken;

[0154] Step S3, measuring the resistance between the B part and the D part by the detection device 10, and the measurement value is y3, wherein y3 comprises R2+R e +R t , R2 is the electronic resistance from the B part to the C part;

[0155] The height of the broken position is calculated according to the following formula:

[0156] R1+R2=y1(2)

[0157] R1+R e +R t =y2(3)

[0158] R2+R e +R t =y34)

[0159] Solving the equation group (2), (3) and (4), the value of R1 is (y1+y2-y3) / 2, and the value of R2 is (y1-y2+y3) / 2;

[0160] The positions of the A part, the B part and the C part satisfy the following relationship:

[0161] L1+L2=L (5)

[0162] L1 / L2=R1 / R2 (6)

[0163] In combination with the values of R1 and R2 and equations (5) and (6), L1=L×(y1+y2-y3) / 2y1 and L2=L×(y1-y2+y3) / 2y1 are obtained, wherein L is the distance from the A part to the B part, L1 is the vertical distance from the C part to the A part, L2 is the vertical distance from the C part to the B part, and L1=L×(y1+y2-y3) / 2y1 and L2=L×(y1-y2+y3) / 2y1.

[0164] The leakage detection system provided by the embodiments can calculate the height of the rupture position of the conductive layer in the protective film according to the data detected by the detection device, such as the resistance between the A part and the B part, the resistance between the A part and the E part, and the resistance between the B part and the E part. In some embodiments, the electrolyte includes a neutral system electrolyte, an alkaline system electrolyte and an acidic system electrolyte, which are stored in an electrolyte pool and connected to the liquid flow battery or the electro-fuel body through a pipeline.

[0165] Further, the acidic system electrolyte includes VO2 + / VO 2+ , V 3+ / V 2+ , Fe 3+ / Fe 2+ , Cr 3+ / Cr 2+ , Mn 3+ / Mn 2+ , the neutral system electrolyte includes Br2 / Br - , the alkaline system electrolyte includes Fe(CN)6 3- / Fe(CN)6 4- or quinone compounds, and these electrolytes can react with the outer wall of the rock and corrode the outer wall of the rock.

[0166] In addition, the potential difference φ C between the C part and the D part satisfies the following Nernst equation:

[0167] (7)

[0168] (8)

[0169] wherein φ θ is the standard electrode potential of the active material, R is the ideal gas constant, T is the electrolyte temperature, n is the number of electrons of the reaction, and F is the Faraday constant.o,C C is the concentration of the oxidant at the C section, C r,C C is the concentration of the reducing agent at the C section, C o,D C is the concentration of the oxidant at the D section, C r,D C is the concentration of the reducing agent at the D section.

[0170] According to (6) and (7), the potential difference φ C -φ D is calculated between the C section and the D section.

[0171] (9)

[0172] When the concentrations of the electrolyte are uniform, and the concentrations of the oxidant and the reducing agent at the C section and the D section are equal, the potential difference φ C -φ D between the loop detection conductor 5 and the conductive layer is 0. Generally, because the underground space is large, when the height difference is large, the solution will be slightly stratified, so the concentration difference of the active substances between the C section and the D section will be partially different, thereby causing the potential difference φ C -φ D to generate a potential difference slightly higher than 0 (generally less than 0.5 volts).

[0173] The leak detection method provided by the application can calculate the height of the rupture position of the conductive layer contained in the protective film by detecting the resistance between the A section and the E section by the detection device and detecting the resistance between the B section and the E section by the detection device.

[0174] The following will be described in conjunction with specific embodiments.

[0175] Embodiment 1

[0176] Figures 3 to 4 FIG. 1 is a structural schematic diagram of a leak detection system provided by the embodiment of the application, which comprises an electrolyte storage container 7, an electrolyte, a detection device 10, and a loop detection conductor 5.

[0177] Specifically, at least one side wall of the electrolyte storage container 7 is provided with the protective film provided by the embodiment of the application, and the electrolyte is stored in the electrolyte storage container 7.

[0178] The end of the conductive layer 4 contained in the protective film at the top of the electrolyte storage container 7 is set as the A section, and the end of the conductive layer 4 contained in the protective film at the bottom of the electrolyte storage container 7 is set as the B section.

[0179] One end of the loop detection conductor 5 is set as the D section and is inserted below the liquid level of the electrolyte, and the other end is set as the E section and is arranged above the liquid level of the electrolyte.

[0180] The detection device 10 comprises a first conductor 11, a second conductor 12, a third conductor 13, a first switch 14, a second switch 15 and a third switch 17, the first conductor 11 is connected with the A part, the second conductor 12 is connected with the B part, the third conductor 13 is connected with the E part, the detection device 10 is connected with the first conductor 11, the second conductor 12 and the third conductor 13 respectively, and is used for detecting the resistance between the A part and the B part, the resistance between the A part and the E part and the resistance between the B part and the E part respectively.

[0181] In the leak detection system, when the anticorrosion layer 3 is intact, the conductive layer 4 is isolated from the electrolyte, and there is no contact between them. At this time, the loop detection conductor 5 cannot form a loop with the conductive layer 4, and is in an open circuit state. Therefore, the voltage and resistance between the conductive layer and the loop detection conductor 5 tend to infinity. When the anticorrosion layer 3 is broken, the conductive layer 4 and the electrolyte are in contact, which produces a potential difference. Then, a voltage (usually less than 0.5V) and a measurable resistance are generated between the conductive layer 4 and the loop detection conductor 5.

[0182] In the leak detection system, when the first switch 14 and the second switch 15 are closed, and the third switch 16 is not closed, the detection device 10, the A part, the first conductor 11, the second conductor 12 and the B part form a first loop, and the resistance between the A part and the B part is detected.

[0183] In the leak detection system, when the first switch 14 and the third switch 16 are closed, and the second switch 15 is not closed, the detection device 10, the electrolyte, the A part, the first conductor 11, the third conductor 13, the C part and the E part form a second loop. The detection device can detect the resistance between the A part and the E part.

[0184] In the leak detection system, when the second switch 15 and the third switch 16 are closed, and the first switch is not closed, the detection device 10, the electrolyte, the B part, the second conductor 12, the third conductor 13 and the E part form a third loop. The detection device 10 can detect the resistance between the B part and the E part.

[0185] In the leak detection system, when the anticorrosion layer 3 is intact, the conductive layer 4 is isolated from the electrolyte, and there is no contact between them. At this time, the loop detection conductor 5 cannot form a loop with the conductive layer 4, and is in an open circuit state. Therefore, the voltage and resistance between the conductive layer 4 and the loop detection conductor 5 tend to infinity. When the anticorrosion layer 3 is broken, the conductive layer 4 and the electrolyte are in contact, which produces a potential difference. Then, a voltage (usually less than 0.5V) and a measurable resistance are generated between the conductive layer 4 and the loop detection conductor 5. Figures 2 to 4A schematic diagram for detecting the position of the broken anticorrosion film layer provided in the embodiments of the present application, wherein the detection principle of the height of the broken position is as follows: the distance between A part and B part is L, which includes the distance L1 between A part and C part, the distance L2 between B part and C part, and the resistance between the top end A part and B part of the conductive film layer is R1+R2, which can be measured by a resistance tester, and the measurement value is y1, wherein R1 is the electronic resistance from A part to C part, and R2 is the electronic resistance from B part to C part, wherein L1 / L2=R1 / R2, since the distance L between A part and B part is a known quantity, if the values of R1 and R2 can be measured, the values of L1 and L2 can be calculated, so as to obtain the distance between C part and A part and B part. Before the anticorrosion layer 3 is broken, the conductive layer 4 and the loop detection conductor 5 are in an open circuit state, and the resistance value and the voltage are both infinite, when the anticorrosion layer 3 is broken, the conductive layer 4 and the electrolyte are in contact with each other to generate a potential difference, and then a voltage (usually lower than 0.5V) and a measurable resistance are generated between the conductive layer 4 and the loop detection conductor 5.

[0186] The detection device, A part, the first conductor 11, the second conductor 12 and B part in the leak detection system of the embodiments of the present application form a first loop, and the detection of the resistance between A part and B part is completed.

[0187] The detection device, the electrolyte, A part, the first conductor 11, the third conductor 13, C part and E part in the leak detection system of the embodiments of the present application form a second loop, and the detection device can detect the resistance between A part and E part.

[0188] The detection device 10, the electrolyte, B part and E part in the leak detection system of the embodiments of the present application form a second loop, and the detection device 10 can detect the resistance between B part and E part.

[0189] The potential difference between the conductive layer 4 and the electrolyte is the Nernst electrode potential φ of the active electric pair C , the potential difference between the loop detection conductor 5 and the electrolyte is the Nernst electrode potential φ of the active electric pair D , and the voltage between D part and C part S is (φ C -φ D ).

[0190] First loop detection: the resistance value between A part and B part is measured by the alternating current impedance method (detection is performed through the first loop), and the measurement value is y1.

[0191] Second loop detection: the resistance value between E part and A part is measured by the alternating current impedance method (detection is performed through the second loop), and the measurement value is y2, and the resistance value includes R1+R e +R twhere R1 is the electronic resistance from A to C, R e is the ionic resistance from C to D, and R t is the electronic resistance from D to E.

[0192] Third loop detection: the resistance of E and B is measured by AC impedance method (through the third loop), the measured value is y3, and the resistance value contains R2+R e +R t , where R2 is the electronic resistance from B to C, R e is the ionic resistance from the rupture position C to D, and R t is the electronic resistance from D to E. Through the above measurement, the following relationship can be obtained:

[0193] R1+R2=y1(1)

[0194] R1+R e +R t =y2(2)

[0195] R2+R e +R t =y3(3)

[0196] Solving the above three equations can obtain the value of R1 as (y1+y2-y3) / 2, and the value of R2 as (y1-y2+y3) / 2.

[0197] On the other hand, the top end A and the bottom end B of the conductive film layer to the rupture position C satisfy the following relationship:

[0198] L1+L2=L(4)

[0199] L1 / L2=R1 / R2(5)

[0200] Combining the values of R1 and R2 and equations (4) and (5), we can get L1=L* (y1+y2-y3) / 2y1, L2=L* (y1-y 2+ y3) / 2y1, and L is a known quantity when designing. y1, y2, and y3 are the measured values of resistance. When the corrosion protection layer is ruptured, the rupture position can be accurately calculated by the detection loop designed by the system. The vertical distance from C to A is L* (y1+y2-y3) / 2y1, and the vertical distance from C to B is L* (y1-y2+y3) / 2y1.

[0201] In addition, the potential difference φC between the conductive layer 4 and the electrolyte satisfies the following Nernst equation:

[0202] (6)

[0203] (7)

[0204] wherein φ θ is the standard electrode potential of the active material, R is the ideal gas constant, T is the temperature of the electrolyte, n is the number of electrons of the reaction, and F is the Faraday constant. C o,C is the concentration of the oxide at the breaking position C, C r,C is the concentration of the reduction at C, C o,D is the concentration of the oxide at D, C r,D is the concentration of the reduction at the bottom end D of the loop detection conductor.

[0205] According to (6) and (7), the potential difference φ C -φ D between the loop detection conductor 5 and the conductive layer 4 can be calculated as:

[0206] (8)

[0207] When the concentrations of the electrolyte are uniform everywhere, such as the concentrations of the oxide and the reduction at C and D are equal, the potential difference φ C -φ D between the loop detection conductor and the conductive layer is 0. Generally, due to the large underground space, when the height difference is large, the solution will be slightly stratified, so there will be some difference in the concentration of the active material between C and D, which will cause φ C -φ D to generate a potential difference slightly higher than 0 (generally less than 0.5 volts).

[0208] Example 2

[0209] In this example, Figure 1 a protective film is provided, which comprises a conductive film layer and an anticorrosion film layer combined with each other, and the anticorrosion film layer is in contact with the electrolyte. This example designs a 100MWh electric fuel energy storage system, which adopts V 3+ / V 2+ and VO2 + / VO 2+The sulfuric acid solution is used as electrolyte, the vanadium ion concentration is 1M, the energy density of the electrolyte is 17Wh / L, two adjacent underground salt caves with a volume of 12000 cubic meters are used as electrolyte storage spaces, before placing the electrolyte, the silicon-titanium oxide composite anti-corrosion gel is sprayed on the smooth rock wall surface as a bonding film layer, the conductive coating containing carbon powder is further coated on the silicon-titanium oxide bottom coating, and the conductive film layer is formed after solidification, and finally the special epoxy resin is coated on the conductive film layer as an outer anti-corrosion film layer. A graphite rod is placed in the electrolyte as a loop detection conductor, and through about 15 times of coating, the thickness of the coating is about 2 cm, and the salt cave on one side is placed with V 3+ / V 2+ The sulfuric acid solution is used as negative electrolyte, and the other salt cave is placed with VO2 + / VO 2+ The sulfuric acid solution is used as positive electrolyte. When the outer anti-corrosion film layer is broken, a voltage difference will occur between the conductive film layer and the loop detection conductor graphite rod, which will send an alarm, and the resistance measurement can detect the position of the coating breakage, providing information for subsequent coating repair. It should be pointed out that although the outer epoxy resin anti-corrosion coating has been broken at this time, the bottom layer of silicon-titanium oxide can still isolate the electrolyte from reacting with the rock wall.

[0210] Example 3

[0211] Iron-chromium flow battery energy storage system, the system uses Fe 3+ / Fe 2+ and Cr 3+ / Cr 2+ hydrochloric acid solution as electrolyte, using iron ion and chromium ion mixed mode for liquid storage, the concentration of iron ion and chromium ion is 1.5M, the energy density of the electrolyte is 12Wh / L, two adjacent underground salt caves with a volume of 8400 cubic meters are used as electrolyte storage spaces, before placing the electrolyte, the silicon-titanium oxide composite anti-corrosion gel is sprayed on the smooth rock wall surface as a bonding film layer, the conductive coating containing carbon nanotubes is further coated on the bonding film layer surface of the silicon-titanium oxide, and finally the special phenolic resin is coated on the conductive film layer surface as an anti-corrosion film layer, a graphite rod is placed in the electrolyte as a loop detection conductor 5, through about 10 times of coating, the thickness of the protective film is about 5mm, and the salt cave on one side is placed with Cr 3+ / Cr 2+ / Fe 2+ hydrochloric acid solution as negative electrolyte, and the other salt cave is placed with Fe 3+ / Fe 2+ / Cr 3+The hydrochloric acid solution is used as the positive electrode storage liquid cavity. When the corrosion-resistant film layer is broken, a voltage difference is generated between the conductive film layer and the loop detection conductor 5 graphite rod, and an alarm is issued. The protective film and the electrolyte of the present application are detected by using the leak detection system and leak detection method described in Example 1, and the height of part C can be detected by resistance measurement, which provides information for subsequent film layer repair. It should be pointed out that although the corrosion-resistant film layer has been broken at this time, the underlying silicon-titanium oxide can still isolate the electrolyte from reacting with the rock wall.

[0212] Example 4

[0213] In this embodiment, a 10MWh alkaline quinone organic flow battery energy storage system is designed. The negative electrode side uses 2,6-dihydroxyanthraquinone as the potassium hydroxide solution as the electrolyte, and the positive electrode side uses the potassium ferricyanide-containing potassium hydroxide solution as the electrolyte. The concentration of 2,6-dihydroxyanthraquinone is 0.5M, and the concentration of potassium ferricyanide is 0.4M, and the energy density of the electrolyte is 6.8Wh / L. Two 0.3 million cubic meters of salt caves are used as underground rock caves as electrolyte storage spaces. Before placing the electrolyte, a silicon-titanium oxide composite corrosion-resistant gel is sprayed on the smooth rock wall surface as a bonding film layer, a conductive paint containing iron powder is further coated on the silicon-titanium oxide bottom coating, and a special phenolic resin is finally coated on the conductive paint as a corrosion-resistant film layer. A 316 stainless steel rod is placed in the electrolyte as a loop detection conductor 5. Through about 20 times of coating, the thickness of the film layer is about 10mm. One side of the salt cave places the 2,6-dihydroxyanthraquinone solution as the negative electrode storage liquid cavity, and the other side of the salt cave places the potassium ferricyanide as the positive electrode storage liquid cavity. When the corrosion-resistant layer 3 is broken, a voltage difference is generated between the conductive film layer and the loop detection conductor 5 stainless steel, and an alarm is issued. The protective film and the electrolyte of the present application are detected by using the leak detection system and leak detection method described in Example 1, and the height of part C can be detected by resistance measurement, which provides information for subsequent film layer repair. It should be pointed out that although the corrosion-resistant film layer has been broken at this time, the underlying silicon-titanium oxide can still isolate the electrolyte from reacting with the rock wall.

[0214] Example 5

[0215] The specific implementation method is as follows. First, according to the capacity of the energy storage system, the energy density of the electrolyte, the space idle rate, and the diameter of the drill bit, the required drilling depth is calculated.

[0216] The required drilling depth can be calculated according to the capacity of the energy storage system, and the formula is as follows:

[0217] (1)

[0218] Wherein, E is the energy of the electrolyte to be stored (watt-hour), n is the number of storage tanks, e is the energy density of the electrolyte (watt-hour / cubic meter), η is the storage space allowance, U is the utilization rate of the electrolyte, and d is the diameter of the drill bit (meter).

[0219] After the drilling is completed, the hole wall and the hole bottom are covered with a foam buffer layer, then a metal mesh structure is added inside the foam buffer layer, finally a shaped thin layer of plastic shell is placed inside the metal mesh structure, and finally the electrolyte is added to the inside of the plastic shell.

[0220] The structure of the leak detection system is shown in Figure 2 The connecting wire between the loop detection conductor and the metal mesh is connected. When the thin layer of resin is intact, the circuit is in an open state, and the resistance is infinite. Once the resin layer is broken, the loop detection conductor, the electrolyte and the metal mesh form a loop, the resistance will be reduced to the ohm level, and a lower voltage will be generated. It needs to be emphasized that although the resin layer is broken at this time, the electrolyte has contacted the porous conductive mesh, but due to the isolation of the foam layer, the electrolyte has not contacted the soil, effectively isolating the reaction between the soil and the electrolyte.

[0221] This embodiment designs a 1MWh electric fuel system, which uses V 3+ / V 2+ and VO2 + / VO 2+ sulfate solution as electrolyte, vanadium ion concentration is 1.7M, energy density of electrolyte is 30Wh / L, design allowance of underground space is 30%, utilization rate of electrolyte is 80%, diameter of drill bit is 2.5m, and through calculation, each of the positive and negative electrodes needs one storage well, wherein the positive side drill well mainly places VO2 + / VO 2+ sulfate solution, and the negative side drill well mainly places V 3+ / V 2+ sulfate solution, and the depth of each side of the drill well is 5.9m. Polyurethane foam material is used as the foam material close to the soil layer, stainless steel mesh is used as the metal mesh structure, polypropylene is used as the thin layer of resin, and graphite rod is used as the loop detection conductor.

[0222] Example 6

[0223] The drilling depth is calculated by the same method as in Example 5.

[0224] This embodiment designs a 100KWh iron-chromium flow battery energy storage system, which uses Fe 3+ / Fe 2+ and Cr 3 + / Cr 2+hydrochloric acid solution as electrolyte, using iron ions and chromium ions mixed mode for storage, concentration of 1.5M, electrolyte energy density of 22Wh / L, underground space design allowance of 30%, electrolyte utilization rate of 70%, drilling head diameter of 2 meters, through the calculation of each need a positive and negative storage well, the positive side of the well mainly placed Fe 3+ / Fe 2+ / Cr 3+ hydrochloric acid electrolyte, negative side mainly placed Cr 3+ / Cr 2+ / Fe 2+ hydrochloric acid electrolyte, each side of the drilling depth of 1.5 meters. Polystyrene foam material as the foam material close to the soil layer, copper mesh as the metal mesh structure, polyvinyl chloride as the thin resin layer, graphite rod as the loop detection conductor.

[0225] Example 7

[0226] The same method as in example 5 to calculate the drilling depth.

[0227] This embodiment designs a set of 10KWh vanadium air electric fuel energy storage system, the system uses V 3+ / V 2+ as electrolyte, air as the positive side of the active material, vanadium ion concentration of 2M, electrolyte energy density of 64Wh / L, underground space design allowance of 30%, electrolyte utilization rate of 70%, drilling head diameter of 1 meter, electrolyte energy density of 64Wh / L, underground space design allowance of 30%, negative side of the electrolyte drilling depth of 0.4 meters. Polystyrene foam material as the foam material close to the soil layer, stainless steel mesh as the metal mesh structure, polyvinyl chloride as the thin resin layer, graphite rod as the loop detection conductor.

[0228] Example 8

[0229] The same method as in example 5 to calculate the drilling depth.

[0230] The embodiment designs a set of 10KWh alkali quinone organic flow battery energy storage system, the negative side of the system uses 2,6-dihydroxy anthraquinone as the potassium hydroxide solution as electrolyte, the positive side uses the potassium ferrocyanide containing potassium hydroxide solution as electrolyte. The concentration of 2,6-dihydroxy anthraquinone is 0.5M, and the concentration of potassium ferrocyanide is 0.4M, and the energy density of the electrolyte is 6.8Wh / L. The diameter of the drilling head is 1m, the design free space of the underground space is 30%, the drilling depth of the negative side electrolyte is 3.8m, and the drilling depth of the negative side electrolyte is 3.8m. Polyethylene foam material is used as the foam material close to the soil layer, titanium mesh is used as the metal mesh structure, polyvinyl chloride is used as the thin layer resin layer, and stainless steel rod is used as the loop detection conductor.

[0231] The above only is the preferred embodiment of the present application, and does not limit the present application, any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A leak detection system, characterized in that, The invention includes an underground space electrolyte storage container or a method thereof, comprising an electrolyte storage container, an electrolyte, a detection device, a first conductor, a second conductor, a third conductor, and a circuit detection conductor; wherein, a protective film is provided on the inner wall surface of the underground space electrolyte storage container for storing the electrolyte, the protective film comprising a conductive layer and an anti-corrosion layer bonded together, and the anti-corrosion layer being for contacting the electrolyte; At least one area of ​​the inner wall of the underground space electrolyte storage container is provided with a protective film, and the end of the conductive layer of the protective film located at or near the top of the electrolyte storage container is designated as part A, and the end of the conductive layer of the protective film located at or near the bottom of the electrolyte storage container is designated as part B. The electrolyte is stored in the electrolyte storage container and is in direct contact with the anti-corrosion layer; One end of the circuit detection conductor is designated as part D and inserted below the surface of the electrolyte, while the other end is designated as part E and positioned above the surface of the electrolyte. The first conductor is connected to part A, the second conductor is connected to part B, and the third conductor is connected to part E. The detection device is connected to the first conductor, the second conductor, and the third conductor respectively, and is used to detect the resistance between part A and part B, the resistance between part A and part E, and the resistance between part B and part E respectively. The preparation method includes: calculating the required drilling depth based on the capacity of the underground space electrolyte storage container, the energy density of the electrolyte, the space idle rate, and the diameter of the drill bit, and drilling the ground to obtain an underground cavity; The required drilling depth can be calculated based on the capacity of the electrolyte storage container in the underground space, using the following formula: （1） Where E represents the energy of the electrolyte to be stored, measured in watt-hours; n is the number of storage tanks; e represents the energy density of the electrolyte, measured in watt-hours per cubic meter. η represents the empty space in the liquid storage area; U represents electrolyte utilization rate; d is the drill bit diameter, in meters; The protective membrane is installed in at least one area on the inner wall surface of the underground cavity to form the electrolyte storage container for the underground space.

2. The leak detection system as described in claim 1, characterized in that, The anti-corrosion layer comprises a composite layer formed by one or two layers of anti-corrosion coating or resin layer; and / or The thickness of the anti-corrosion layer is 400~800μm.

3. The leak detection system as described in claim 2, characterized in that, The material forming the resin layer includes at least one of polyvinyl chloride, polypropylene, or polytetrafluoroethylene; and / or The anti-corrosion coating includes any one or two layers of epoxy resin film or phenolic resin film, or a composite film formed by two of them.

4. The leak detection system as described in claim 3, characterized in that, The coating used to form the epoxy resin film includes component A and component B, wherein... Component A includes: 30-50 parts epoxy resin Amine curing agent composition: 10-30 parts Component B includes: 0.1 to 1 part of polysiloxane leveling agent 0.01~0.1 parts of polysiloxane-based foaming agent Dispersant 0.1~1.5 parts 2-10 parts toughening agent 3-8 parts talcum powder 3-11 parts zinc sulfate 3-8 parts aluminum tripolyphosphate 3-8 parts mica powder 6-15 parts barite powder 3-8 parts of titanium dioxide or / and The coating used to form the phenolic resin film includes component C and component D, wherein... The C component includes: 40-52 parts of cashew phenol modified phenolic resin 20-23 parts alkyd resin 10-16 parts of titanium dioxide The D component includes: 7.3 parts of pine resin solvent oil 0.8 parts wetting agent 0.5 parts of anti-settling dispersant 0.2 parts defoamer 0.15 parts of oxidative polymerization drying agent 0.05 parts of anti-skinning agent.

5. The leak detection system according to any one of claims 1-4, characterized in that, The conductive layer comprises a composite layer formed by one or two of the following: a conductive coating, a metal mesh, a metal foam layer, and a metal fiber layer; and / or The thickness of the conductive layer is 400~800μm.

6. The leak detection system as described in claim 5, characterized in that, The metal mesh, metal foam layer, and metal fiber layer contain the same or different metals, including at least one of copper, stainless steel, tungsten, titanium, nickel-chromium, molybdenum, and silver.

7. The leak detection system as described in claim 5, characterized in that, The coating used to form the conductive coating comprises the following components: 1-40 parts of conductive powder; Preservative 10-65 parts; 2-25 parts of reactive diluent; 4-27 parts of curing agent; Curing accelerator: 0.25-4 parts; Defoamer 0.1~1 part; Plasticizer 2-15 parts.

8. The leak detection system according to claim 7, characterized in that, The conductive powder comprises at least one of conductive polymers, conductive carbon materials, and conductive metals; and / or The curing agent includes diaminodiphenylmethane; and / or The curing accelerator includes phenol; and / or The defoamer used in the coating to form the conductive coating includes at least one of methyl silicone oil and dimethyl silicone oil; The plasticizer includes at least one of dibutyl phthalate, dioctyl phthalate, triphenyl phosphate, or tricresyl phosphate.

9. The leak detection system according to any one of claims 1-4, 6, and 7, characterized in that, It also includes an isolation layer, which is laminated between the conductive layer and the inner wall surface of the electrolyte storage container that supports the protective membrane.

10. The leak detection system as described in claim 9, characterized in that, The isolation layer includes an adhesive film layer or a foam layer.

11. The leak detection system according to claim 1, characterized in that, The circuit detection conductor includes one of the following: graphite rod, graphite composite material, copper rod, and 316 stainless steel rod.

12. A leak detection method, characterized in that, A leak detection method, including the leak detection system as described in any one of claims 1-11, comprises the following steps: The resistance between part A and part B is measured using the detection device, and the measured value is y1; The resistance between part A and part E is measured using the detection device, and the measured value is y2, where y2 includes R1 + R e +R t R1 is the electronic resistance from section A to section C, R e R is the ion resistance from section C to section D. t The electronic resistance is from part E to part B, where part C is the location where the anti-corrosion layer is cracked; The resistance between part E and part B is measured using the detection device, and the measured value is y3, where y3 includes R2 + R e +R t R2 is the electronic resistance from section B to section C; The height of the fracture location can be calculated using the following formula: R1+R2=y1(2) R1+R e +R t =y2(3) R2+R e +R t =y3(4) Solving the system of equations (2), (3) and (4), we obtain the value of R1 as (y1+y2-y3) / 2 and the value of R2 as (y1-y2+y3) / 2; The positions of parts A, B, and C satisfy the following relationship: L1 + L2 = L(5) L1 / L2=R1 / R2(6) Combining the values ​​of R1 and R2 with equations (5) and (6), we obtain L1=L×(y1+y2-y3) / 2y1, L2=L×(y1-y2+y3) / 2y1, where L is the distance from part A to part B, L1 is the vertical distance from part C to part A, and L2 is the vertical distance from part C to part B.

Images