CN218539384U - An electrodialysis seawater desalination synergistically electrocatalytically degrades organic sewage and produces H2O2 device - Google Patents

Abstract

The utility model discloses an electrodialysis sea water desalination is in coordination with electro-catalysis degradation organic sewage and produce H ₂ O ₂ The device belongs to the field of coastal industrial water treatment. The utility model comprises a platinum sheet anode which is connected with a direct current power supply, a carbon black gas diffusion cathode and an anion-cation exchange membrane pair between the two electrodes. Under the drive of external voltage, chloride ions in a desalting chamber formed by the anion-cation exchange membrane pair migrate into the anode chamber, and sodium ions migrate into the cathode chamber to realize desalting; the platinum sheet anode generates hypochlorous acid to degrade organic sewage through chlorine evolution reaction; cathode electro-catalytic reduction of oxygen to H by carbon black gas diffusion ₂ O ₂ . The reaction device can realize high-efficiency, low-consumption and stable treatment of organic sewage and seawater and synchronously generate industrial finished products H ₂ O ₂ The cost of coastal industrial water can be reduced, and the method has wide application prospect.

Description

An electrodialysis seawater desalination synergistically electrocatalytically degrades organic sewage and produces H2O2 device

technical field

The utility model belongs to the field of coastal industrial water treatment, and more specifically relates to a device for electrodialysis seawater desalination and electrocatalysis for degrading organic sewage and producing H ₂ O ₂ .

Background technique

The shortage of water resources in my country's coastal areas has become increasingly prominent. Nearly 90% of the more than 50 coastal cities under the jurisdiction of 11 coastal provinces (or municipalities) have water shortage problems, which has seriously affected the sustainable economic and social development of coastal areas. Dense population, developed industry, large water demand, and serious water pollution are the important reasons for the shortage of water resources in coastal areas. Coastal areas are rich in seawater resources, and the discharge of industrial sewage is large, of which organic sewage is the main discharge. Seawater desalination and advanced treatment and reuse of organic sewage are two important ways to solve water shortage in coastal areas. At present, seawater desalination and organic sewage treatment are often carried out separately under different scenarios. Seawater desalination is usually treated by technologies such as reverse osmosis, multi-stage flash evaporation, and multi-effect evaporation, which have problems such as high pressure, high energy consumption, and difficult treatment of concentrated brine; organic sewage treatment is usually treated by biochemical methods, and the complex components of sewage cause biochemical Poor performance, dealing with high energy consumption and other issues. Obviously, separate treatment of the two faces problems such as high plant construction and operating costs, poor water treatment effect, and difficult treatment of brine.

Synchronous treatment of organic sewage and seawater is expected to solve the problems faced by separate treatment of the two. The current synchronous treatment technology for organic sewage and seawater is to effectively combine microbial fuel cells or photocatalytic fuel cells with electrodialysis membrane stack desalination (Science of Total Environment, 2020, 748, 141046; Applied Catalysis B: Environmental, 2021, 284, 119745), the electrodialysis membrane stack is built between the two electrodes of the microbial fuel cell or photocatalytic fuel cell, and the electric energy generated by the microbial fuel cell or photocatalytic fuel cell is used as the desalination power of the electrodialysis membrane stack to realize organic sewage degradation and seawater desalination . Chinese patent CN111816902A discloses a capacitive microbial desalination battery device and method for chemical tail water treatment, which belongs to the technical field of water resources treatment. The battery device includes an anode chamber, a desalination chamber and a cathode chamber separated by anion and cation exchange membranes respectively; the anode is made of carbon material, and the cathode is made of hollow carbon fiber-carbon film capacitor layer, titanium base layer, waterproof layer and catalytic layer arranged in sequence. The formed hollow carbon fiber-carbon film capacitor electrode; the anode and the cathode are connected by an external circuit. However, microbial fuel cells use microorganisms to decompose to generate current, which is complex in operation and unstable in power generation, and microorganisms are sensitive to special pollutants, making it difficult to deal with highly toxic and refractory pollutants.

The photogenerated electrons and holes of photocatalytic fuel cells are easy to recombine, and the photoelectric conversion efficiency of semiconductor electrodes is low, so it is difficult to effectively drive the system to operate by photocatalytic electricity generation alone. The composite reaction device constructed with microbial fuel cells, photocatalytic fuel cells and reverse electrodialysis membrane stacks has major defects in the simultaneous treatment of organic sewage and seawater, making it difficult for commercial application. Therefore, it is of great significance to design a simple reaction device with simple structure, stable operation and high efficiency, which can treat various organic sewage and seawater.

After retrieval, the patent publication number is CN105236527A, and the publication date is January 13, 2016. The invention discloses a three-dimensional electrode device and a green electrochemical treatment method for synchronous and continuous desalination and organic pollutant removal of wastewater. The device includes a cation exchange resin unit, an anion exchange resin unit, an electrode chamber unit and several OFR electrocatalytic units; sodium sulfate is placed in the electrode chamber unit as the electrode chamber circulation fluid; the ion exchange resin unit is equipped with ion exchange resin fillers, anion The exchange membrane is placed in the cathode area, and the cation exchange membrane is placed in the anode area; the OFR electrocatalytic unit is equipped with OFR special filler; the OFR electrocatalytic unit in the middle of the device is the formation and collection area of concentrated water; the wastewater passes through the OFR electrocatalytic unit, cation The exchange resin unit, OFR electrocatalytic unit, anion exchange resin unit, and the final discharge device achieve the purpose of synchronous desalination and organic matter removal. The device uses three-dimensional electrode catalysis to generate hydroxyl radicals to remove organic pollutants, and uses electrodialysis and ion exchange resins for desalination. The target water body to be treated is saline organic sewage. Its disadvantages are that the device has a complex structure and relatively high construction cost. Before operation, the water body needs to be aerated, and the fillers used need to be pretreated. The operation is relatively complicated and the efficiency is low.

Contents of the invention

1. The problem to be solved

Aiming at the problem of unstable operation and low efficiency of existing organic sewage and seawater _synchronous treatment devices, the utility model provides an electrodialysis seawater desalination synergistically electrocatalytically degrades organic sewage and produces _H2O2 . The device operates stably and efficiently, and can be used for seawater desalination and treatment of different kinds of organic sewage to produce H ₂ O ₂ .

2. Technical solution

In order to solve the above problems, the technical scheme adopted in the utility model is as follows:

An electrodialysis seawater desalination synergistically electrocatalytically degrades organic sewage and produces H ₂ O ₂ device, including a power supply, a cathode, a cathode chamber where the cathode reaction occurs, and a cation exchange membrane adjacent to the cathode chamber; an anode, an anode chamber where the anodic reaction occurs, and an adjacent Anion exchange membrane in the anode compartment; desalination compartment, located between the anion exchange membrane and the cation exchange.

Wherein, the cathode chamber and the anode chamber contain electrolyte, the anode chamber contains organic sewage, and the desalination chamber contains seawater, and the NaCl concentration in the seawater is 35 g/L, which is also suitable for the NaCl concentration of 15g/L-45g/L seawater or NaCl solution, in actual use, the NaCl concentration is unlimited. The electrolyte can be K ₂ SO ₄ , or Na ₂ SO ₄ , as long as it meets the requirement of electrical conductivity.

The device of the utility model can be used for the degradation of ampicillin and other organic pollutants, as long as it can be degraded by hypochlorous acid.

Further, the power supply is a DC power supply with a voltage of 3-5V and a current of 20-90mA, wherein the voltage needs to be greater than 1.36V. The reason is that the reaction of chlorine ions being oxidized to generate chlorine gas is under the condition of a voltage greater than 1.36V. Only then can it be realized. It is provided by solar, wind or hydropower, can make full use of the vast coastal outdoor environment, and install corresponding solar, wind or hydropower facilities to charge the DC power supply to improve the continuous stability and service life of the entire device. The power supply can also be AC, but requires a matching rectifier to convert to DC for operation.

Further, the cathode is a gas diffusion electrode, and the electrode material can be platinum carbon, activated coke, graphite, carbon black, etc., preferably a carbon black gas diffusion electrode, and titanium mesh is used as an electrode in the carbon black gas diffusion electrode The skeleton is composed of carbon black and high-purity conductive graphite powder. In addition, other gas diffusion electrodes can be used to realize the electrocatalytic production of H ₂ O ₂ . The carbon black gas diffusion electrode contains carbon The element is an excellent electrode material for generating H ₂ O ₂ , non-toxic, low-cost, and the porous material of the electrode can allow the oxygen in the air to independently penetrate into the cathode solution and participate in the cathode reduction reaction, in which electrolysis of water generates H ₂ O ₂ The potential is 0.695V, and the cathodic reduction reaction formula is 2H ⁺ +2e ^- +O ₂ →H ₂ O ₂ .

Further, the anode is a chlorine analyzing electrode, a platinum plate electrode can be selected, and other chlorine analyzing electrodes such as a titanium electrode, a lead dioxide electrode, a titanium coated ruthenium iridium electrode, etc. can also be used.

Further, the shape of the anode is a plate, and may also be a sheet, a rod, or a mesh.

Further, the anion exchange membrane and the cation exchange membrane are arranged in pairs to form an electrodialysis membrane, and the number of the electrodialysis membranes is one or more groups, and multiple sets of ion exchange membranes are stacked in pairs, and are carried out according to the salinity load. match.

In the prior art, microbial fuel cells are used to desalinate seawater and degrade organic sewage synergistically. For example, in patent CN111816902A, sodium ions and chloride ions migrate to the cathode and anode respectively under the action of osmotic pressure and microbial electricity generation voltage. The microorganisms in the anode swallow the substances to be degraded through metabolism, and release electrons and protons. After the electrons are collected, they are output through the electrodes to generate voltage. The voltage output of the microorganisms is low and unstable, and the driving effect is poor. Chloride ions migrating into the anode chamber cannot be consumed, and combine with protons produced by microbial metabolism to form hydrochloric acid, resulting in an increase in the acidity of the solution, which is not conducive to the survival of microorganisms and affects the degradation and electricity generation effects. In addition, microbial fuel cells use microorganisms to directly convert chemical energy in organic matter into electrical energy. There is a preparation period before operation and a recovery period after operation, making the operation complicated.

Therefore, the utility model adopts electrodialysis coupling electrochemical catalysis. During use, under the joint drive of osmotic pressure and external voltage, the chloride ions in the desalination chamber migrate to the anode chamber, and the sodium ions migrate to the cathode chamber to realize seawater desalination. Due to osmotic pressure and ion migration driven by microbial electricity production and photocatalytic electricity production, the electric energy output is more stable, the driving force is stronger, and the catalytic reaction is more efficient. Among them, chlorine ions are oxidized in the anode chamber to generate chlorine gas, and chlorine gas is dissolved in water to generate hypochlorous acid, which is generated by electrocatalytic chlorine analysis reaction to generate hypochlorous acid to degrade organic sewage; electrons migrate to the carbon black gas diffusion cathode through the external circuit, and the Oxygen is reduced to H ₂ O ₂ . Using this device for seawater desalination and synergistic catalytic degradation of organic sewage to produce H ₂ O ₂ can effectively solve the problems of slow start-up, low treatment efficiency, unstable operation, high toxicity and refractory organic sewage of microbial desalination devices and photocatalytic desalination devices, etc. Problems, to achieve simultaneous high-efficiency, low-consumption, and long-term stable treatment of organic sewage and seawater.

3. Beneficial effect

Compared with the prior art, the beneficial effects of the utility model are:

(1) A device for electrodialysis seawater desalination and electrocatalysis to degrade organic sewage and produce H ₂ O ₂ in this utility model can effectively solve the problems of slow start-up, low treatment efficiency, unstable operation, and difficulty in microbial desalination devices and photocatalytic desalination devices. To deal with problems such as highly toxic and refractory organic sewage, and realize simultaneous high-efficiency, low-consumption, and long-term stable treatment of organic sewage and seawater;

(2) An electrodialysis seawater desalination synergistically electrocatalytically degrades organic sewage and produces H ₂ O ₂ device of the utility model. It has a wide range of applications and can treat industrial organic sewage with poor water quality and serious organic pollution. Produces H ₂ O ₂ ; the effect of electrocatalytic treatment is remarkable, the removal rate of ampicillin is >90%, the desalination rate of seawater is >50%, and the output of H ₂ O ₂ is as high as 3g/L;

(3) An electrodialysis seawater desalination synergistically electrocatalytically degrades organic sewage and produces H ₂ O ₂ device of the utility model, which can effectively avoid the construction cost of high pipe network, complex organic sewage and seawater treatment process facilities, and the treatment of concentrated brine It has the characteristics of short process, low investment, low operation and maintenance costs, etc. It is expected to be vigorously promoted and applied in the future-oriented low-carbon water treatment market;

(4) An electrodialysis seawater desalination synergistically electrocatalytically degrades organic sewage and produces H ₂ O ₂ device of the utility model, which can be used as industrial water for industrial organic sewage regeneration and desalination of seawater in coastal industrial cities, and for the industrial water treatment of these cities Provide theoretical basis and technical reference.

Description of drawings

The technical scheme of the utility model will be further described in detail below in conjunction with the drawings and embodiments, but it should be known that these drawings are only designed for the purpose of explanation, and therefore are not intended to limit the scope of the utility model. Furthermore, unless otherwise indicated, the drawings are only intended to conceptually illustrate the architectural configurations described herein and are not necessarily drawn to scale.

Fig. 1 is the operation schematic diagram of the utility model reactor;

Figure 2 shows the operation effect of the reaction device under different voltages, (a) ampicillin removal rate, (b) seawater desalination rate, (c) H ₂ O ₂ output, (d) output current;

Figure 3 shows the operation effect of the reaction device under different ampicillin concentrations, (a) ampicillin removal rate, (b) seawater _desalination rate, (c) _H2O2 production, (d) output current, where the voltage is 4V;

Figure 4 shows the operation effect of the reaction device under different seawater salinity, (a) ampicillin removal rate, (b) seawater desalination rate, (c) H ₂ O ₂ output, (d) output current.

Detailed ways

The following detailed description of exemplary embodiments of the invention refers to the accompanying drawings, which form a part hereof, and in which are shown by way of example exemplary embodiments in which the invention can be practiced. While these exemplary embodiments have been described in sufficient detail to enable those skilled in the art to practice the invention, it should be understood that other embodiments can be implemented and the invention can be utilized without departing from the spirit and scope of the invention. Various changes. The following more detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but only for illustration and not to limit the description of the characteristics and characteristics of the present invention, in order to propose the implementation of the present invention. The best mode, and enough to enable those skilled in the art to implement the utility model. Accordingly, the scope of the invention is to be limited only by the appended claims.

The platinum sheet is inserted into the anode chamber as the anode, and the prepared carbon black gas diffusion electrode is inserted into the cathode chamber as the cathode. An anion exchange membrane is fixed between the anode chamber and the desalination chamber, and an anion exchange membrane is fixed between the cathode chamber and the desalination chamber. The cation exchange membrane constitutes a three-chamber reaction device. Among them, the anode chamber contains refractory organic sewage and 0.05M potassium sulfate electrolyte, the cathode chamber contains 0.05M potassium sulfate electrolyte, and the desalination chamber contains 35g/L sodium chloride solution. The anode and the cathode are connected through an external circuit and are driven by the external power supply to generate electricity through a catalytic reaction. The anode undergoes a chlorine analysis reaction to generate hypochlorous acid to degrade organic sewage. The cathode generates H ₂ O ₂ through an electrocatalytic oxygen reduction reaction, and is driven by a voltage The intermediate desalination chamber desalinizes seawater to realize the degradation of organic sewage, desalination of seawater and production of H ₂ O ₂ .

Examples 1-6

The platinum sheet is inserted into the anode chamber as the anode, and the carbon black gas diffusion electrode is inserted into the cathode chamber as the cathode, and the two electrodes are connected with a wire and an external DC power supply is connected. A cation exchange membrane and an anion exchange membrane are respectively fixed between the anode chamber and the cathode chamber, wherein the cation exchange membrane is close to the side of the cathode chamber. The anode chamber contains 200mg/L ampicillin (AMP) and 0.05M potassium sulfate solution, the cathode chamber contains 0.05M potassium sulfate solution, and the desalination chamber contains 35g/L sodium chloride solution. After connecting the external power supply, the degradation, desalination, output current and H ₂ O ₂ production performance of the reaction device under different voltages were investigated.

The reaction device in this example can effectively degrade organic sewage, desalinate seawater and produce H ₂ O ₂ after running for 3 hours, but the treatment effects are quite different under different external voltages. The specific results are shown in Figure 2 and Table 1.

Table 1 Embodiment 1-6 operation effect

running result Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Applied voltage 0V 1V 2V 3V 4V 5V AMP removal rate 0% 0% 41.6% 70.7% 90.1% 92.4% Output current 0mA 0mA 2-3mA 20-26mA 29-48mA 40-90mA NaCl removal rate 18.6% 20% 24.7% 48.4% 74.2% 92% H₂O₂yield 0mg/L 0mg/L 165mg/L 1793mg/L 3083mg/L 3588mg/L

As shown in Table 1, when the external voltage is 0, 1, 2, 3, 4, 5V, the removal rate of AMP is 0%, 10%, 41.6%, 70.7%, 90.1%, 92.4%; the output current is respectively 0mA, 0mA, 2-3mA, 20-26mA, 29-48mA, 40-90mA; NaCl removal rates were 18.6%, 20%, 24.7%, 48.4%, 74.2%, 92%; H ₂ O ₂ yields were 0mg/L, 0mg/L, 165mg/L, 1793mg/L, 3083mg/L, 3588mg/L. The voltage is zero, the desalination chamber only relies on osmotic pressure for desalination, and the voltage generated by ion migration _is not enough for chlorine evolution reaction and oxygen reduction reaction, so there is no AMP degradation and _H2O2 generation in the system. When the voltage was 1 _V , the chlorine evolution reaction voltage was not reached, so there was no AMP removal, no electron migration and _H2O2 generation. When the voltage is 3-5V, the chlorine analysis reaction and oxygen reduction reaction voltage are reached. The higher the voltage, the faster the ion migration in the desalination chamber, and the faster the catalytic reaction in the cathode chamber and the anode chamber. Therefore, the removal rate of AMP, NaCl and The higher _{the H2O2} production.

Therefore, in consideration of AMP degradation, desalination in the desalination chamber, H ₂ O ₂ production, and electricity consumption, the external voltage is above 2V, preferably above 3V, and more preferably 3-5V.

Example 7-9

The test was carried out according to the method of Example 1, only the concentration of AMP was changed, as shown in Figure 3 and Table 2 for details.

Table 2 embodiment 7-9 running effect

running result Example 7 Example 8 Example 9 AMP concentration 100mg/L 200mg/L 300mg/L AMP removal rate 100% 91% 77.5% Output current 26-50mA 27-55mA 26-52mA NaCl removal rate 64.7% 62.1% 62.5% H₂O₂yield 3053mg/L 3823mg/L 3410mg/L

As shown in Table 2, when the AMP concentration is 100mg/L, 200mg/L, and 300mg/L, the removal rate of AMP is 100%, 91%, and 77.5%, respectively, and the AMP removal rate decreases with the increase of AMP concentration; The output currents are 26-50mA, 27-55mA, and 26-2mA respectively, and the output current of the reaction device is not affected by the concentration of AMP; the removal rates of NaCl are 64.7%, 62.1%, and 62.5%, respectively, and the removal rates of NaCl in the desalination chamber are not affected by the concentration of AMP Influence; H ₂ O ₂ yields were 3053mg/L, 3823mg/L, and 3410mg/L respectively, and H ₂ O ₂ yields were basically not affected by AMP concentration. The reason is that the anode in the reaction device is a chlorine analysis reaction, and the concentration of AMP only affects its reaction with hypochlorous acid, and does not affect the _anode chlorine analysis reaction _. no effect.

Therefore, in consideration of AMP degradation, desalination in desalination chamber, H ₂ O ₂ production, and electricity consumption, the concentration of AMP should be above 100 mg/L, preferably 200 mg/L.

Examples 10-13

Test according to the method of Example 1, only change the salinity of seawater, that is, the NaCl concentration, as shown in Figure 4 and Table 3 for details.

Table 3 embodiment 10-13 running effect

When the seawater salinity is 15g/L, 25g/L, 35g/L, 45g/L, the removal rate of AMP is 61.1%, 76.5%, 91%, 92.5%, respectively, and the removal rate of AMP increases with the increase of seawater salinity and increase; the output current is 25-32mA, 27-51mA, 27-55mA, 34-70mA respectively, and the output current of the reaction device increases with the increase of seawater salinity; the NaCl removal rate is 88.3%, 81.1%, 62.5% respectively , 60.5 _{% ,} NaCl _removal rate decreases with the increase of _seawater salinity; increased by the increase. The increase of seawater salinity will increase the osmotic pressure between the seawater and the solution in the cathode chamber and the anode chamber, accelerate the migration speed of ions in the desalination chamber to the cathode chamber and the anode chamber, increase the concentration of chloride ions in the anode, promote the chlorine analysis reaction, and improve The degradation rate of organic matter is improved, and the migration speed of electrons to the cathode is accelerated, thereby increasing the output current of the device and the production of H ₂ O ₂ .

Therefore, in consideration of AMP degradation, desalination in the desalination chamber, H ₂ O ₂ production, and electricity consumption, the salinity of seawater is above 15g/L, preferably 35-45g/L.

The electrodialysis seawater desalination synergistically electrocatalytically degrades organic sewage and produces H ₂ O ₂ device of the utility model, and effectively combines the electrocatalysis degraded sewage and the electrodialysis seawater desalination. The utility model can desalinate the seawater in the desalination chamber under the drive of a lower voltage, convert the chloride ions in the seawater into hypochlorous acid to degrade the organic sewage through electrocatalysis, and simultaneously generate industrial finished product H ₂ O ₂ , realizing industrial Synchronous high-efficiency, low-consumption, stable and resource-based treatment of organic sewage and seawater.

Claims (9)

1. Electrodialysis sea water desalination and electrocatalysis synergetic organic sewage degradation and H production ₂ O ₂ An apparatus, comprising a power source; the cathode comprises a cathode, a cathode chamber in which cathode reaction occurs and a cation exchange membrane close to the cathode chamber, wherein electrolyte is contained in the cathode chamber; the device comprises an anode, an anode chamber for generating anode reaction and an anion exchange membrane close to the anode chamber, wherein the anode chamber is filled with electrolyte and organic sewage; and the desalting chamber is positioned between the anion exchange membrane and the cation exchange membrane, seawater is contained in the desalting chamber, the anode of the power supply is connected with the anode, and the cathode of the power supply is connected with the cathode.

2. The method of claim 1, wherein the electrodialysis sea water desalination is cooperated with electrocatalysis to degrade organic sewage and produce H ₂ O ₂ The device is characterized in that the power supply is a direct current power supply, and the voltage of the power supply is 3-5V.

3. The method of claim 2, wherein the electrodialysis sea water desalination is cooperated with electrocatalysis to degrade organic sewage and produce H ₂ O ₂ The device is characterized in that the anode is selected from chlorine evolution electrodes, and the chlorine evolution electrodes are one of platinum sheet electrodes, titanium electrodes, lead dioxide electrodes and titanium ruthenium-coated iridium electrodes.

4. The method of claim 3, wherein the electrodialysis desalination of seawater is combined with the electrocatalysis to degrade organic wastewater and produce H ₂ O ₂ The device is characterized in that the shape of the anode is one or more of plate, sheet, rod and net.

5. The method of claim 4, wherein the electrodialysis sea water desalination is cooperated with electrocatalysis to degrade organic sewage and produce H ₂ O ₂ The device is characterized in that the cathode is a gas diffusion electrode, and the material of the gas diffusion electrode is selected from one of platinum carbon, activated coke, graphite and carbon black.

6. The electrodialysis seawater desalination and electrocatalysis of claim 5Chemical degradation of organic sewage and production of H ₂ O ₂ The device is characterized in that the cathode is a carbon black gas diffusion electrode, and a titanium wire mesh is used as an electrode framework in the carbon black gas diffusion electrode.

7. The method of claim 6, wherein the electrodialysis sea water desalination is cooperated with electrocatalysis to degrade organic sewage and produce H ₂ O ₂ The device is characterized in that the anion exchange membranes and the cation exchange membranes are arranged in pairs to form electrodialysis membranes, and the number of the electrodialysis membranes is one group or multiple groups.

8. The method of claim 7, wherein the electrodialysis sea water desalination is cooperated with electrocatalysis to degrade organic sewage and produce H ₂ O ₂ The device is characterized in that the concentration of NaCl in the seawater is 15-45 g/L.

9. The method of claim 8, wherein the electrodialysis desalination of seawater is combined with the electrocatalysis to degrade organic wastewater and produce H ₂ O ₂ Device, characterized in that the electrolyte is selected from K ₂ SO ₄ And Na ₂ SO ₄ To (3) is provided.

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