High-efficiency energy circulation system based on hydrochloric acid electrolysis and working method thereof

Abstract

The invention belongs to the technical field of electrochemical energy storage, and particularly relates to an efficient energy circulation system based on hydrochloric acid electrolysis and a working method thereof. And in the energy storage stage, hydrogen and chlorine evolution reactions are respectively carried out on two poles of the hydrochloric acid electrolysis hydrogen and chlorine evolution system. Chlorine generated by the anode of the hydrochloric acid electrolysis hydrogen and chlorine evolution system is introduced into the chlorine storage device, and hydrogen generated by the cathode of the system is introduced into the hydrogen storage device. Meanwhile, the chlorine storage device is communicated with the cathode of the hydrogen-chlorine fuel cell; and the hydrogen storage device is communicated with the anode of the hydrogen-chlorine fuel cell. In the energy release stage, hydrogen and chlorine react to generate hydrogen chloride, and energy is released. The overpotential in the process is small, so that the energy storage and release efficiency is high, and efficient circulation of the system and efficient storage of energy can be realized.

Description

Technical Field

[0001] This invention belongs to the field of electrochemical energy storage technology, specifically relating to a high-efficiency energy cycle system based on hydrochloric acid electrolysis and its working method. Background Technology

[0002] The use of new energy power generation and scientific energy storage are of great significance for achieving the "dual carbon" goal. Through technological innovation, new energy power generation, such as photovoltaic power generation, wind power generation, and hydropower generation, has made significant progress. However, it still suffers from drawbacks such as intermittency, instability, and dependence on the environment. Although these new energy sources can generate electricity, the aforementioned shortcomings make it difficult to integrate the generated electricity into the existing power system. Achieving large-scale, high-efficiency energy storage is crucial for the efficient utilization of fluctuating renewable energy sources.

[0003] Using water electrolysis to produce green hydrogen, and then using fuel cells to release electricity when energy is needed, is an effective method for large-scale, cross-seasonal use of renewable energy, but the overall energy utilization efficiency is not high.

[0004] This application is submitted in order to address the aforementioned issues. Summary of the Invention

[0005] In the process of developing this invention, the applicant discovered that the main reason for the low energy efficiency of the above-mentioned process is the large overpotential of the oxygen evolution reaction, often exceeding 200mV; the overpotential of the oxygen reduction reaction also exceeds 0.3V. However, the applicant's research revealed that the overpotentials of the chlorine evolution and chlorine reduction reactions are much smaller, making them better alternative reactions. Therefore, this invention is proposed.

[0006] The purpose of this invention is to provide an energy cycle system based on hydrochloric acid electrolysis, which uses a high-performance catalyst to achieve a good energy cycle and can solve the problem of new energy power storage to the greatest extent.

[0007] The chlorine evolution reaction is the anodic reaction in the hydrochloric acid electrolysis hydrogen chlorine evolution system. As a high-energy-consuming anodic reaction in the traditional chlor-alkali industry, its overpotential is small, and the overpotential of the reverse reaction is also small. The inventive point of this application is to discover that the chlorine evolution reaction can be matched with the hydrogen redox reaction to form a more efficient energy cycle storage system.

[0008] In the process of generating electricity using new energy sources, excess electrical energy not transmitted to the grid is efficiently electrolyzed with hydrochloric acid solution to obtain chlorine and hydrogen, converting intermittent electrical energy into chemical energy for storage. When the grid needs electricity, the chlorine and hydrogen produced in the above process are used as fuel in a hydrogen-chlorine fuel cell. Using a high-performance catalyst, high-performance discharge is achieved while hydrochloric acid is produced, realizing the circular flow of energy.

[0009] This application provides an energy cycle system based on hydrochloric acid electrolysis, the energy cycle system comprising: a hydrochloric acid storage device 1, an electrolytic hydrochloric acid hydrogen and chlorine evolution system 2, a hydrogen storage device 5, a chlorine storage device 6, and a hydrogen-chlorine fuel cell 7;

[0010] The hydrochloric acid storage device 1 is connected to the anode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2 via a hydrochloric acid input pipe 101, or the hydrochloric acid storage device 1 is connected to both the anode and cathode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2 via the hydrochloric acid input pipe 101. The anode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2 is connected to the chlorine storage device 6, and the chlorine storage device 6 is connected to the cathode of the hydrogen-chlorine fuel cell 7 via a chlorine input pipe 109.

[0011] The cathode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2 is connected to the hydrogen storage device 5, and the hydrogen storage device 5 is connected to the anode of the hydrogen-chlorine fuel cell 7 through the hydrogen input pipe 108.

[0012] The cathode of the hydrogen-chlorine fuel cell 7 is also connected to the hydrochloric acid storage device 1.

[0013] When the hydrochloric acid storage device 1 is connected to the anode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2 through the hydrochloric acid input pipe 101, protons in the electrolyte can permeate through the proton exchange membrane to the cathode side of the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2, and finally hydrogen is obtained at the cathode.

[0014] Preferably, the energy recycling system further includes a chlorine separation device 4;

[0015] The anode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2 is connected to the chlorine separation device 4 through the chlorine / hydrochloric acid output pipeline 102, and the chlorine separation device 4 is connected to the chlorine storage device 6 through the chlorine output pipeline 105.

[0016] Preferably, the chlorine storage device 6 is equipped with a chlorine compression device, or a chlorine compression device is provided between the chlorine output pipe 105 and the chlorine storage device 6 to pressurize and liquefy the chlorine.

[0017] Preferably, the lower part of the chlorine separation device 4 is connected to the hydrochloric acid storage device 1 through a second hydrochloric acid reflux pipe 107.

[0018] Preferably, the energy cycle system further includes a hydrogen separation device 3;

[0019] The cathode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2 is connected to the hydrogen separation device 3 through the hydrogen / hydrochloric acid output pipeline 103, and the hydrogen separation device 3 is connected to the hydrogen storage device 5 through the hydrogen output pipeline 104.

[0020] Preferably, the lower part of the hydrogen separation device 3 is connected to the hydrochloric acid storage device 1 through the first hydrochloric acid reflux pipe 106.

[0021] Preferably, the energy cycle system further includes a chlorine / hydrogen chloride separation device 8;

[0022] The cathode of the hydrogen-chlorine fuel cell 7 is connected to the chlorine / hydrogen chloride separation device 8 via a chlorine / hydrogen chloride output pipe 111. The upper part of the chlorine / hydrogen chloride separation device 8 is connected to the chlorine storage device 6 via a chlorine return pipe 112, and the lower part of the chlorine / hydrogen chloride separation device 8 is connected to the hydrochloric acid storage device 1.

[0023] Preferably, the energy recycling system further includes a hydrochloric acid recovery and purification device 9;

[0024] The lower part of the chlorine / hydrogen chloride separation device 8 is connected to the hydrochloric acid recovery and purification device 9 through a hydrochloric acid / saturated brine transport pipeline 113. One end of the hydrochloric acid recovery and purification device 9 is connected to the hydrochloric acid storage device 1 through a hydrogen chloride reflux pipeline 115, and the other end of the hydrochloric acid recovery and purification device 9 is connected to the chlorine / hydrogen chloride separation device 8 through a saturated brine reflux pipeline 114.

[0025] Preferably, the anode of the hydrogen-chlorine fuel cell 7 is also connected to the hydrogen storage device 5 via a hydrogen return pipe 110.

[0026] The aforementioned pipeline can be equipped with pumps, valves, and flow meters.

[0027] The electrolytic hydrochloric acid hydrogen and chlorine evolution system 2 also includes a corrosion-resistant liquid pump, a power supply system, and a tail gas drying and dehydration device.

[0028] The second aspect of this application provides a method for operating the energy cycle system based on hydrochloric acid electrolysis described in the first aspect, the method comprising:

[0029] Using electrical energy connected to the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2, and using the hydrochloric acid provided in the hydrochloric acid storage device 1 as the electrolyte, a chlorine evolution reaction and a hydrogen evolution reaction occur to obtain chlorine and hydrogen. The chlorine output from this process is sent to the chlorine storage device 6 for storage and later use, and the hydrogen output from this process is sent to the hydrogen storage device 5 for storage and later use.

[0030] Chlorine storage device 6 and hydrogen storage device 5 are respectively fed into the cathode and anode of the hydrogen-chlorine fuel cell 7. Chlorine and hydrogen react in the hydrogen-chlorine fuel cell 7 to produce hydrogen chloride and generate electricity. The hydrogen chloride flows back to the hydrochloric acid storage device 1 for recycling.

[0031] Preferably, the chlorine gas is pressurized and liquefied within the chlorine storage device 6, or is pressurized and liquefied before being sent to the chlorine storage device 6. Preferably, the pressure of pressurization and liquefaction is equal to or greater than 2 MPa.

[0032] Preferably, the anode in the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2 is a mixed metal oxide electrode.

[0033] The hybrid metal oxide electrode comprises a conductive substrate and a hybrid metal oxide loaded on the conductive substrate, wherein the molecular formula of the hybrid metal oxide is M. x Ru 1-x O2;

[0034] Where M represents two or more of Ti, Sn, Sb, Nb, Zr, V, Co, Fe, and Ni;

[0035] x is the mole fraction of all metals in M ​​and M x Ru 1-x The ratio of the mole fractions of all metals in O2, x = 20-70%.

[0036] The above "multiple" refers to two or more types, such as three, four, five, six, seven, eight, or nine.

[0037] Preferably, the mixed metal oxide electrode has a mud-crack-like surface, which is composed of nanoparticles with a size of 5 to 100 nanometers.

[0038] Preferably, the metal elements in the mixed metal oxide are uniformly dispersed.

[0039] Preferably, the conductive substrate is a porous carbon material or a porous metal material.

[0040] The above-mentioned method for preparing a mixed metal oxide electrode includes the following steps:

[0041] (1) Prepare alcohol solutions of different metals respectively;

[0042] The alcohol solutions of the different metals include ruthenium and M.

[0043] Wherein, M is two or more of Ti, Sn, Sb, Nb, Zr, V, Co, Fe, and Ni;

[0044] (2) Mix the alcohol solutions of different metals prepared in step (1) to obtain a mixed solution in which the different metals are evenly dispersed. The molar ratio of ruthenium and M in the mixed solution is 1-x:x, where x = 20% to 70%.

[0045] Then, a polymer with polydentate ligands is added to the mixed solution, and the mixture is heated and stirred to allow it to fully react with the solution to be coated.

[0046] (3) The coating solution obtained in step (2) is brushed onto the conductive substrate and heated to dry. This coating-heating and drying process is performed 1-4 times in total.

[0047] (4) The coated conductive substrate is then calcined in air and then cooled to room temperature in air. This calcination-cooling process is performed 1-4 times in total.

[0048] (5) The coated conductive substrate is then calcined in air and cooled to room temperature in the furnace to obtain a mixed metal oxide electrode.

[0049] Preferably, the polymer with polydentate ligands added in step (2) is selected from one or more of polyvinyl alcohol, polyethylene glycol, polyethylene diamine and polyvinylpyrrolidone.

[0050] Preferably, in step (2), the ratio of the polymer with polydentate ligands to the total metal in the solution to be coated is (60-240 mg):(0.5-2 mmol).

[0051] Preferably, in step (2), the heating and stirring temperature is 50-90℃ and the time is 2-8h;

[0052] The drying temperature in step (3) is 50-90℃ and the drying time is 1-20 min.

[0053] The calcination temperature in step (4) is 400-600℃ and the calcination time is 1-20min.

[0054] The calcination temperature in step (5) is 400-600℃ and the calcination time is 0.5-3h.

[0055] Preferably, the conductive substrate is a porous conductive substrate, specifically a porous carbon material or a porous metal material. Porous metal materials can be titanium felt, titanium mesh, etc. Porous carbon materials can be carbon paper, carbon cloth, etc.

[0056] Preferably, the hydrochloric acid electrolysis hydrogen and chlorine evolution system 2 further includes: titanium-based anode and cathode plates, and a proton exchange membrane electrode. The proton exchange membrane electrode comprises a proton exchange membrane and an anode catalyst layer and a cathode catalyst layer on both sides of the proton exchange membrane.

[0057] Titanium-based anode and cathode plates are corrosion-resistant, and therefore can withstand electrolyte corrosion during use.

[0058] The proton exchange membrane can be selected from Nafion perfluorosulfonic acid membrane, Hancheng Hyproof enhanced perfluorosulfonic acid proton exchange membrane, or fumapem perfluorosulfonic acid / polytetrafluoroethylene copolymer membrane.

[0059] The cathode catalyst is selected from noble metal catalysts, such as carbon-supported platinum, ruthenium, iridium, palladium and other metals.

[0060] The electrolyte in the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2 is 0.1–10 mol / L. -1 For hydrochloric acid of a certain concentration, the catalyst loading on the electrode is 2–10 mg / cm³. -2 .

[0061] Preferably, the hydrogen-chlorine fuel cell 7 includes: titanium-based anode and cathode plates, and proton exchange membrane electrodes.

[0062] The proton exchange membrane can be, for example, Nafion perfluorosulfonic acid membrane, Hancheng Hyproof enhanced perfluorosulfonic acid proton exchange membrane, or Fumapem perfluorosulfonic acid / polytetrafluoroethylene copolymer membrane.

[0063] The cathode catalyst can be any existing precious metal catalyst, such as carbon-supported platinum, ruthenium, iridium, palladium, etc.

[0064] The anode catalyst can also be an existing noble metal catalyst, such as carbon-supported platinum, ruthenium, iridium, palladium and other metals.

[0065] Preferably, the catalyst loading is 2–10 mg cm⁻¹ -2 .

[0066] According to the Hume-Rothery rule, when the atomic size difference of the components is less than 14-15%, it favors the formation of solid solutions with higher solubility (solubility limit); when it is greater than 15%, it is unfavorable for the formation of solid solutions. Modulating the electronic structure of electrocatalysts by doping with other elements of suitable size and electronegativity is a common and effective way to improve electrocatalytic performance. Therefore, this application develops a highly efficient and low-cost electrocatalytic chloride ion oxidation catalyst by doping ruthenium dioxide with relatively low-cost non-noble metal oxides.

[0067] The hybrid metal oxide electrode is prepared using a sol-gel method. This electrode belongs to the category of low-noble-metal hybrid oxide electrodes. This electrode does not use the noble metal iridium and reduces the amount of the relatively inexpensive noble metal ruthenium. While significantly reducing the preparation cost of the DSA electrode (Dimensionally Stable Anode), it exhibits superior electrochemical activity and chlorination selectivity compared to commercial DSAs, and demonstrates good stability. Furthermore, the electrode preparation method is simple, enabling mass production and application.

[0068] In the course of pursuing this application, the applicant discovered that:

[0069] O2 / O in common hydrogen-oxygen fuel cells with four-electron transfer 2-The reaction overpotential is generally above 150mV. This potential is completely consumed in order to drive the reaction and cannot be utilized.

[0070] Compared to O2 / O 2- The reaction in a hydrogen-chlorine fuel cell, Cl2 / Cl - The overpotential of the reaction is only 0-20 mV, Cl2 / Cl - The redox pair exhibits rapid kinetics and excellent reversibility. Simultaneously, Cl₂ / Cl₂... - The theoretical redox potential is as high as 1.36V vs. SHE, and the energy storage capacity can reach 755mAh g. -1 It is the vanadium oxide (VO2) currently used in redox flow batteries. + / VO 2+ More than twice that of (226mAh / g).

[0071] Therefore, the hydrogen-chlorine fuel cell of this application has less energy loss compared to the hydrogen-oxygen fuel cell.

[0072] Compared with the prior art, this application has the following advantages:

[0073] 1. This application discloses an energy cycle system based on hydrochloric acid electrolysis, involving the hydrochloric acid electrolysis hydrogen and chlorine evolution reactions, and hydrogen-chlorine fuel cell technology. It is the first application to combine a hydrochloric acid electrolysis hydrogen and chlorine evolution system with a hydrogen-chlorine fuel cell, utilizing electrical energy to efficiently electrolyze hydrochloric acid to obtain chlorine and hydrogen respectively, converting electrical energy into chemical energy for storage. When electrical energy is needed, the chlorine and hydrogen generated in the above process are used as fuel, passing through the hydrogen-chlorine fuel cell to react and obtain hydrochloric acid, thus converting chemical energy into electrical energy. The hydrochloric acid obtained from the reaction can be recycled as a raw material for the hydrochloric acid electrolysis hydrogen and chlorine evolution system. Due to the small overpotential in the above process, the overpotentials for chlorine and hydrogen evolution can be as low as 0-20mV, resulting in high energy storage and release efficiency and enabling efficient system recycling.

[0074] 2. In the energy cycle system of this application, chlorine is easily liquefied and stored, and hydrogen storage methods are mature. Therefore, the system of this application has the advantages of high energy storage density, convenient transportation of compressed gas energy storage, and high material and energy cycle efficiency.

[0075] 3. In particular, this application also discloses a high-performance mixed metal oxide electrode. The inventors have found that doping ruthenium dioxide with metal elements has significant advantages in this electrode: (1) In terms of activity, appropriate doping with metals such as Ti, Sn, Sb, Nb, Zr, V, Co, Fe, and Ni can adjust the electronic structure of oxygen active sites, which is beneficial to their adsorption of chlorine, thereby reducing the free energy of the rate-determining step and improving the catalytic activity of the electrode. However, too much or too little element doping does not achieve the desired effect: if the element doping is too low (i.e., x < 20%), the change in the performance of the ruthenium dioxide electrode is not obvious, and its preparation cost is not significantly reduced, so its practical application value is not great; if the element doping is too high (i.e., x > 70%), the crystal structure of ruthenium dioxide is prone to large distortion, the electrode material will split, impurity phases will be generated, and the performance will rapidly decay.

[0076] (2) Regarding stability, the reason why traditional ruthenium dioxide-based catalysts are unstable under long-term oxidation conditions is mainly because ruthenium dioxide is easily over-oxidized into soluble species and dissolved in the electrolyte at the oxidation potential. However, by incorporating non-noble metals into ruthenium dioxide nanomaterials, the covalent nature of the Ru-O bond is weakened due to the introduction of the dopant metal, resulting in ruthenium being in a lower valence state and suppressing its over-oxidation at the oxidation potential during the reaction process. This allows the electrode material to exhibit good stability when applied to the electrocatalytic chloride ion oxidation reaction. During the stability test, the galvanostatic polarization curve can still remain stable for a long time under high current density operating conditions. Moreover, in the preparation process, the highest valence compounds of doped metals such as Ti, Sn, and Sb are used as transition metal sources. The high temperature and high pressure liquid environment allows them to be fully oxidized, and their oxides have strong stability, thus playing a stable role in regulating the ruthenium sites in the electrolyte, thereby improving the stability of the electrode. Attached Figure Description

[0077] Figure 1 The Zr obtained in Examples 1, 3, 5, and 7 respectively 0.6 Sb 0.1 Ru 0.3 O2 electrode, Zr 0.6 V 0.1 Ru 0.3 O2 electrode, Sn 0.6 Nb 0.1 Ru 0.3 O2 electrode, Sn 0.6 Ti 0.1 Ru 0.3 SEM image of the O2 electrode.

[0078] Figure 2 It is Zr 0.6 Sb 0.1 Ru0.3 Surface elemental distribution diagram of O2 electrode.

[0079] Figure 3 It is Zr 0.6 V 0.1 Ru 0.3 Surface elemental distribution diagram of O2 electrode.

[0080] Figure 4 It is Sn 0.6 Nb 0.1 Ru 0.3 Surface elemental distribution diagram of O2 electrode.

[0081] Figure 5 It is Sn 0.6 Ti 0.1 Ru 0.3 Surface elemental distribution diagram of O2 electrode.

[0082] Figure 6 It is Zr 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru 0.3 O2, Sn 0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 TEM image of particles on the surface of the O2 electrode.

[0083] Figure 7 The nine curves A, B, C, D, E, F, G, H, and I represent the Zr curves in Example 1. 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru 0.3 O2, Sn 0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 O2, Ti 0.2 Sn 0.2 Sb 0.3 Ru 0.3 O2, Nb 0.2 Zr 0.2 V 0.3 Ru 0.3 O2, Co 0.1 Fe 0.1 Ni 0.1 Ru0.7 O2 electrode, Ti 0.14 Sn 0.07 Sb 0.07 Nb 0.07 Zr 0.07 V 0.07 Co 0.07 Fe 0.0 7Ni 0.07 Ru 0.3 Polarization curves of electrocatalytic chlorine production under acidic conditions using an O2 electrode and a commercial ruthenium-iridium DSA electrode.

[0084] Figure 8 The nine curves A, B, C, D, E, F, G, H, and I represent the Zr curves in Example 1. 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru 0.3 O2, Sn 0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 O2, Ti 0.2 Sn 0.2 Sb 0.3 Ru 0.3 O2, Nb 0.2 Zr 0.2 V 0.3 Ru 0.3 O2, Co 0.1 Fe 0.1 Ni 0.1 Ru 0.7 O2 electrode, Ti 0.14 Sn 0.07 Sb 0.07 Nb 0.07 Zr 0.07 V 0.07 Co 0.07 Fe 0.0 7Ni 0.07 Ru 0.3 Chlorine selectivity histograms for O2 electrode and commercial ruthenium-iridium DSA electrode.

[0085] Figure 9 The five curves A, B, C, D, and E are respectively obtained from Example 2 regarding Zr. 0.6 Sb 0.1 Ru 0.3 O2 electrode, Zr 0.1 Sb 0.1 Ru 0.8 O2 electrode, Zr 0.7Sb 0.1 Ru 0.2 O2 electrode, Zr 0.05 Sb 0.05 Ru 0.9 Polarization curves of electrocatalytic chlorine production using an O2 electrode and a commercial ruthenium-iridium DSA electrode.

[0086] Figure 10 The five curves A, B, C, D, and E are respectively obtained from Example 3 for Zr. 0.6 V 0.1 Ru 0.3 O2 electrode, Zr 0.1 V 0.1 Ru 0.8 O2 electrode, Zr 0.7 V 0.1 Ru 0.2 O2 electrode, Zr 0.05 V 0.05 Ru 0.9 Polarization curves of electrocatalytic chlorine production using an O2 electrode and a commercial ruthenium-iridium DSA electrode.

[0087] Figure 11 The five curves A, B, C, D, and E are respectively obtained from Sn in Example 4. 0.6 Nb 0.1 Ru 0.3 O2 electrode, Sn 0.1 Nb 0.1 Ru 0.8 O2 electrode, Sn 0.7 Nb 0.1 Ru 0.2 O2 electrode, Sn 0.05 Nb 0.05 Ru 0.9 Polarization curves of electrocatalytic chlorine production using an O2 electrode and a commercial ruthenium-iridium DSA electrode.

[0088] Figure 12 The five curves A, B, C, D, and E are respectively obtained from Sn in Example 5. 0.6 Ti 0.1 Ru 0.3 O2 electrode, Sn 0.1 Ti 0.1 Ru 0.8 O2 electrode, Sn 0.7 Ti 0.1 Ru 0.2 O2 electrode, Sn 0.05 Ti 0.05 Ru 0.9 Polarization curves of electrocatalytic chlorine production using an O2 electrode and a commercial ruthenium-iridium DSA electrode.

[0089] Figure 13The five curves A, B, C, D, and E are obtained from the Zr curve in Example 6. 0.6 Sb 0.1 Ru 0.3 O2 electrode, Zr 0.6 V 0.1 Ru 0.3 O2 electrode, Sn 0.6 Nb 0.1 Ru 0.3 O2 electrode, Sn 0.6 Ti 0.1 Ru 0.3 Stability test curves for electrocatalytic chlorine production using O2 electrode and commercial ruthenium-iridium DSA electrode.

[0090] Figure 14 The nine curves A, B, C, D, E, F, G, H, and I represent Zr. 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru 0.3 O2, Sn 0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 O2, Ti 0.2 Sn 0.2 Sb 0.3 Ru 0.3 O2, Nb 0.2 Zr 0.2 V 0.3 Ru 0.3 O2, Co 0.1 Fe 0.1 Ni 0.1 Ru 0.7 O2 electrode, Ti 0.14 Sn 0.07 Sb 0.07 Nb 0.07 Zr 0.07 V 0.07 Co 0.07 Fe 0.07 Ni 0.07 Ru 0.3 Polarization curves of electrocatalytic production of hypochlorous acid under neutral conditions using an O2 electrode and a commercial ruthenium-iridium DSA electrode.

[0091] Figure 15 The nine curves A, B, C, D, E, F, G, H, and I represent Zr. 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6V 0.1 Ru 0.3 O2, Sn 0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 O2, Ti 0.2 Sn 0.2 Sb 0.3 Ru 0.3 O2, Nb 0.2 Zr 0.2 V 0.3 Ru 0.3 O2, Co 0.1 Fe 0.1 Ni 0.1 Ru 0.7 O2 electrode, Ti 0.14 Sn 0.07 Sb 0.07 Nb 0.07 Zr 0.07 V 0.07 Co 0.07 Fe 0.07 Ni 0.07 Ru 0.3 Polarization curves of electrocatalytic hypochlorite production under alkaline conditions using an O2 electrode and a commercial ruthenium-iridium DSA electrode.

[0092] Figure 16 This is a schematic diagram of an energy cycle system based on hydrochloric acid electrolysis.

[0093] Figure 17 This is a schematic diagram of the principle of an energy cycle system based on hydrochloric acid electrolysis.

[0094] Figure 18 In the figure, a represents the electrocatalytic chlorine reduction polarization curves of carbon nanotube-supported Pt clusters, RuO2 electrodes, and commercial ruthenium-iridium DSA electrodes, while b represents the electrocatalytic hydrogen oxidation polarization curves of carbon-supported platinum, carbon-supported iridium, and carbon-supported ruthenium.

[0095] Explanation of reference numerals in the attached figures:

[0096] 1- Hydrochloric acid storage device; 2- Electrolytic hydrochloric acid hydrogen and chlorine evolution system; 3- Hydrogen separation device; 4- Chlorine separation device; 5- Hydrogen storage device; 6- Chlorine storage device; 7- Hydrogen-chlorine fuel cell; 8- Chlorine / hydrogen chloride separation device; 9- Hydrochloric acid recovery and purification device.

[0097] 101 - Hydrochloric acid input pipeline; 102 - Chlorine / hydrochloric acid output pipeline; 103 - Hydrogen / hydrochloric acid output pipeline; 104 - Hydrogen output pipeline; 105 - Chlorine output pipeline; 106 - Hydrochloric acid reflux pipeline; 107 - Hydrochloric acid reflux pipeline; 108 - Hydrogen input pipeline; 109 - Chlorine input pipeline; 110 - Hydrogen reflux pipeline; 111 - Chlorine / hydrogen chloride output pipeline; 112 - Chlorine reflux pipeline; 113 - Hydrochloric acid / saturated brine transport pipeline; 114 - Saturated brine reflux pipeline; 115 - Hydrogen chloride reflux pipeline. Detailed Implementation

[0098] The present application will now be described in further detail with reference to the embodiments.

[0099] Those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be construed as limiting the scope of this application. Where specific techniques or conditions are not specified in the embodiments, they are performed in accordance with the techniques or conditions described in the literature in the field or according to the product manual. Materials or equipment whose manufacturers are not specified are all conventional products that can be obtained by purchase.

[0100] Those skilled in the art will understand that, unless specifically stated otherwise, the singular forms “a,” “an,” “the,” and “the” used herein may also include the plural forms. It should be further understood that the word “comprising” as used in this application's specification means the presence of the stated features, integers, steps, operations, elements, and / or components, but does not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. It should be understood that when we say an element is “connected” to another element, it can be directly connected to the other element, or there may be intermediate elements. Furthermore, the term “connected” as used herein can include wireless connections.

[0101] In the description of this application, unless otherwise stated, "a plurality of" means two or more. The terms "inner," "upper," "lower," etc., indicate the orientation or state relationship based on the orientation or state relationship shown in the drawings, and are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this application.

[0102] In the description of this application, it should be noted that, unless otherwise expressly specified and limited, the terms "installation," "connection," and "equipped with" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium. Those skilled in the art will understand the specific meaning of the above terms in this application according to the specific circumstances.

[0103] It will be understood by those skilled in the art that, unless otherwise defined, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. It should also be understood that terms such as those defined in general dictionaries should be understood to have the meaning consistent with their meaning in the context of the prior art, and should not be interpreted in an idealized or overly formal sense unless defined as herein.

[0104] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60–120 and 80–110 are listed for a specific parameter, it is understood that ranges of 60–110 and 80–120 are also expected. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1–3, 1–4, 1–5, 2–3, 2–4, and 2–5. In this application, unless otherwise stated, the numerical range "a–b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0~5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0105] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions. Unless otherwise specified, all technical features and optional technical features of this application can be combined to form new technical solutions. Unless otherwise specified, all steps of this application can be performed sequentially or randomly, preferably sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, if the method may also include step (c), it means that step (c) can be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0106] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0107] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B".

[0108] In this application, the hydrochloric acid storage device in the energy cycle system is connected to the hydrochloric acid electrolysis hydrogen and chlorine evolution system and the hydrogen-chlorine fuel cell. Hydrochloric acid serves as both a reactant and an electrolyte. During the energy storage phase, hydrogen and chlorine evolution reactions occur at both electrodes of the hydrochloric acid electrolysis hydrogen and chlorine evolution system. Chlorine gas produced at the anode of the system is fed to a chlorine storage device, and hydrogen gas produced at the cathode is fed to a hydrogen storage device. Simultaneously, the chlorine storage device is connected to the cathode of the hydrogen-chlorine fuel cell; the hydrogen storage device is connected to the anode of the hydrogen-chlorine fuel cell. During the energy release phase, hydrogen and chlorine react in the hydrogen-chlorine fuel cell to produce hydrogen chloride, releasing energy. When electrical energy is abundant, this application utilizes electricity to efficiently electrolyze hydrochloric acid to obtain chlorine and hydrogen, converting electrical energy into chemical energy for storage. When electrical energy is needed, the chlorine and hydrogen generated in the above process are used as fuel in the hydrogen-chlorine fuel cell, realizing the conversion of chemical energy into electrical energy. The hydrochloric acid obtained from the reaction can be recycled as a raw material for the hydrochloric acid electrolysis hydrogen and chlorine evolution system. Because the overpotential in the above process is small, the energy storage and release efficiency is high, which can realize the efficient circulation of the system and the efficient storage of energy.

[0109] The carbon nanotube-supported Pt clusters, RuO2 electrodes, and commercial ruthenium-iridium DSA electrodes used in this application are sourced from Sigma-Aldrich.

[0110] Figure 16 This embodiment describes an energy cycle system based on hydrochloric acid electrolysis. The energy cycle system includes: a hydrochloric acid storage device 1, an electrolytic hydrochloric acid hydrogen and chlorine evolution system 2, a hydrogen separation device 3, a chlorine separation device 4, a hydrogen storage device 5, a chlorine storage device 6, and a hydrogen-chlorine fuel cell 7.

[0111] The hydrochloric acid storage device 1 is connected to the cathode and anode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2 via a hydrochloric acid input pipe 101 to supply hydrochloric acid as an electrolyte. The anode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2 is connected to a chlorine storage device 6 to liquefy and store the chlorine gas generated by electrolysis. The chlorine storage device 6 is connected to the cathode of the hydrogen-chlorine fuel cell 7 via a chlorine gas input pipe 109 to supply chlorine gas to the hydrogen-chlorine fuel cell 7.

[0112] The cathode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2 is connected to the hydrogen storage device 5 to store the hydrogen generated by electrolysis. The hydrogen storage device 5 is connected to the anode of the hydrogen-chlorine fuel cell 7 through the hydrogen input pipe 108 to supply hydrogen to the hydrogen-chlorine fuel cell 7.

[0113] The cathode of the hydrogen-chlorine fuel cell 7 is also connected to the hydrochloric acid storage device 1 to recover the hydrochloric acid produced by the battery reaction.

[0114] In this embodiment, the energy recycling system further includes a chlorine separation device 4;

[0115] The anode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2 is connected to the chlorine separation device 4 through the chlorine / hydrochloric acid output pipeline 102, and the chlorine separation device 4 is connected to the chlorine storage device 6 through the chlorine output pipeline 105.

[0116] In this embodiment, the lower part of the chlorine separation device 4 is connected to the hydrochloric acid storage device 1 through the second hydrochloric acid reflux pipe 107, so that the separated liquid hydrochloric acid can be refluxed back to the hydrochloric acid storage device 1.

[0117] In this embodiment, the energy cycle system further includes a hydrogen separation device 3;

[0118] The cathode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system 2 is connected to the hydrogen separation device 3 through the hydrogen / hydrochloric acid output pipeline 103, and the hydrogen separation device 3 is connected to the hydrogen storage device 5 through the hydrogen output pipeline 104.

[0119] In this embodiment, the lower part of the hydrogen separation device 3 is connected to the hydrochloric acid storage device 1 through the first hydrochloric acid reflux pipe 106, so that the separated liquid hydrochloric acid can be refluxed back to the hydrochloric acid storage device 1.

[0120] Of course, it is foreseeable that in some embodiments, the purpose of this application can be achieved without designing the chlorine separation device 4 and the hydrogen separation device 3.

[0121] In this embodiment, the energy cycle system further includes a chlorine / hydrogen chloride separation device 8;

[0122] The cathode of the hydrogen-chlorine fuel cell 7 is connected to the chlorine / hydrogen chloride separation device 8 via a chlorine / hydrogen chloride output pipe 111. The upper part of the chlorine / hydrogen chloride separation device 8 is connected to the chlorine storage device 6 via a chlorine return pipe 112, and the lower part of the chlorine / hydrogen chloride separation device 8 is connected to the hydrochloric acid storage device 1.

[0123] In this embodiment, the energy recycling system further includes a hydrochloric acid recovery and purification device 9;

[0124] The lower part of the chlorine / hydrogen chloride separation device 8 is connected to the hydrochloric acid recovery and purification device 9 through a hydrochloric acid / saturated brine transport pipeline 113. One end of the hydrochloric acid recovery and purification device 9 is connected to the hydrochloric acid storage device 1 through a hydrogen chloride reflux pipeline 115, and the other end of the hydrochloric acid recovery and purification device 9 is connected to the chlorine / hydrogen chloride separation device 8 through a saturated brine reflux pipeline 114.

[0125] Of course, it is foreseeable that in some embodiments, the purpose of this application can be achieved without designing the chlorine / hydrogen chloride separation device 8 and the hydrochloric acid recovery and purification device 9.

[0126] In this embodiment, the chlorine / hydrogen chloride separation device 8 is equipped with a saturated brine washing bottle to absorb hydrogen chloride. The hydrochloric acid recovery and purification device 9 purifies hydrogen chloride by distillation, with the evaporation temperature set at 80-85°C.

[0127] The hydrogen separation unit 3 and the chlorine separation unit 4 can be selected from conventional gas-liquid separation units.

[0128] In this embodiment 1, the chlorine separation device 4 passes through a dehydration device to dry the chlorine before being connected to the chlorine storage device 6 via the chlorine output pipeline 105, and is then pressurized to 2 MPa by a chlorine compression device for liquefaction. The chlorine compression device is a chlorine compressor.

[0129] The hydrogen separation device 3, before being connected to the hydrogen storage device 5 via the hydrogen output pipe 104, passes through a dehydration device to dry the hydrogen. The dehydration device can be a concentrated sulfuric acid bottle washing device. In this embodiment, the anode of the hydrogen-chlorine fuel cell 7 is also connected to the hydrogen storage device 5 via a hydrogen return pipe 110. The hydrogen exhaust gas output from the anode of the hydrogen-chlorine fuel cell 7 does not require removal of hydrochloric acid. During the anode hydrogen oxidation process, only protons are transferred to the cathode and contact with chloride ions obtained from chlorine reduction to form chloride. Hydrogen Hydrogen chloride does not penetrate the membrane and mixes into the hydrogen tail gas at the anode.

[0130] The hydrogen-chlorine fuel cell includes a corrosion-resistant gas flow controller, corrosion-resistant titanium metal electrode plates, a proton exchange membrane electrode, and a chlorine / hydrogen chloride separation device.

[0131] The hydrochloric acid recovery and purification device includes a pH monitor, a hydrochloric acid condensation device, and a tail gas absorption device.

[0132] The gas storage device in the energy cycle system stores chlorine and hydrogen produced by hydrochloric acid electrolysis for later use. When the hydrogen-chlorine fuel cell 7 needs to discharge, the two gases are connected to its chlorine fuel inlet and hydrogen fuel inlet respectively to be delivered to the cathode and anode of the hydrogen-chlorine fuel cell 7. The effect of controllable power generation of the hydrogen-chlorine fuel cell is achieved by a corrosion-resistant gas flow controller.

[0133] Main operating conditions:

[0134] Operating temperature: 20~40℃

[0135] Hydrochloric acid flow rate: 90~130L / h

[0136] Hydrochloric acid electrolysis exhaust gas flow rate: 30~110mL / min (depending on electrolysis current)

[0137] Hydrogen and chlorine main gas pressure: 17518.7~63094.4 N / m 2 (Depends on the electrolysis current)

[0138] Hydrochloric acid concentration: 0.1–10 mol / L -1

[0139] Hydrogen-chlorine fuel cell output current: 20-30A

[0140] Output voltage: 0.6~0.9V

[0141] Output power: 17-20W

[0142] Current density: 0.8~1.2Acm -2

[0143] Energy density: 0.68–0.8 W / cm³ -2

[0144] The working process of the energy cycle system based on hydrochloric acid electrolysis in the example is as follows:

[0145] Using intermittent electrical energy input, it is connected to hydrochloric acid electrolysis system 2, at a rate of 0.1–10 mol / L. -1 Hydrochloric acid is used as the electrolyte, and chlorine and hydrogen evolution reactions occur to produce chlorine and hydrogen gas. The operating conditions are atmospheric pressure, and the liquid flow rates at the anode and cathode are 90–130 L / h respectively. The specific reactions that occur are as follows:

[0146] Anode: 2Cl - -2e - =Cl2;

[0147] Cathode: 2H + +2e - =H2;

[0148] Overall reaction: 2HCl=Cl2+H2;

[0149] The chlorine gas output from this process is sent to the chlorine storage device 6 via chlorine separation device 4 for liquefaction and storage for later use. The liquid hydrochloric acid obtained from chlorine separation device 4 is returned to the hydrochloric acid storage device 1. The hydrogen gas output from this process is sent to the hydrogen storage device 5 via hydrogen separation device 3 for storage and later use. The hydrochloric acid obtained from hydrogen separation device 3 is returned to the hydrochloric acid storage device 1.

[0150] Generally, the oxygen evolution reaction at the anodic apex in water electrolysis is a four-electron transfer reaction, requiring an overpotential of at least 150 millivolts to overcome the reaction energy barrier. In contrast, the chlorine evolution reaction at the anodic apex in hydrochloric acid electrolysis is a two-electron transfer reaction, requiring only an overpotential of 0-20 millivolts to overcome the reaction energy barrier. Therefore, compared to water electrolysis, the hydrochloric acid hydrogen and chlorine evolution system has a higher energy utilization efficiency.

[0151] The hydrogen-chlorine fuel cell operates similarly to the reverse of the above process, under ambient temperature and pressure, with anode and cathode gas flow rates of 30–110 mL / min. Hydrogen and chlorine are derived from the electrolytic deposition of the above process and stored in a hydrogen-chlorine storage device, which is connected to the hydrogen inlet and chlorine inlet of the hydrogen-chlorine fuel cell, respectively. Specifically, hydrogen is oxidized at the anode of the proton exchange membrane electrode, with the chemical reaction being H₂ - 2e⁻. - =2H + Protons are produced and travel through the proton exchange membrane to the cathode of the proton exchange membrane electrode, where they react with chloride ions from chlorine gas to form hydrogen chloride. The chlorine gas is then reduced at the cathode of the proton exchange membrane electrode; the chemical reaction is Cl₂ + 2e⁻. - =2Cl - The overall chemical reaction inside the fuel cell is H2 + Cl2 = 2HCl. The cathode tail gas chlorine and the hydrogen chloride obtained from the reaction are separated by a chlorine / hydrogen chloride separator 8. The obtained chlorine is returned to the chlorine storage device 6, and the obtained hydrogen chloride is processed by a hydrochloric acid recovery and purification device 9. The purified hydrochloric acid is then returned to the hydrochloric acid storage device 1, thus realizing the recycling of materials and energy.

[0152] Figure 17 This is a schematic diagram of an energy cycle system based on hydrochloric acid electrolysis. The diagram illustrates the highly reversible nature of the hydrogen evolution reduction reaction and the hydrogen oxidation reaction, as well as the highly reversible nature of the chlorine evolution oxidation reaction and the chlorine reduction reaction. The combination of these two reactions demonstrates the complete reversibility of the hydrochloric acid electrolysis energy cycle system.

[0153] The overall reaction equation for a hydrogen-chlorine fuel cell is: H₂ + Cl₂ = 2HCl;

[0154] Average voltage of hydrogen-chlorine fuel cells: Ev = 1.36 - 0 = 1.36V;

[0155] The energy produced by 1 mol of hydrogen gas is 1.36V × 96485C = 131219.6J = 36.45Wh. The energy produced by 1kg of H2 (1kg of H2 consumes 35.5kg of Cl2 at the same time) is 1000 / 2 × 36.45 ÷ 1000 = 18.225kWh.

[0156] The specific energy is: 18.225kWh / (1kg+35.5kg)=0.5kWh / kg.

[0157] Therefore, compared with other energy storage methods, this battery has a higher specific energy, as shown in Table 1 below.

[0158] Table 1. Comparison of energy storage density (specific energy) of hydrogen-chlorine fuel cells with other existing energy storage methods

[0159]

[0160] The energy density data for other existing energy storage methods are sourced from patent CN 106785242 B.

[0161] Furthermore, in currently widely studied hydrogen-oxygen fuel cells, the reversible voltage is 1.23V. However, the relatively high overpotential of the oxygen reduction reaction results in an actual discharge potential of only 0.6–0.8V, and a corresponding voltage efficiency of only 49%–65%, leading to a low energy conversion efficiency. In contrast, the near-zero overpotential characteristic of chlorine reduction allows hydrogen-chlorine fuel cells to achieve a higher actual discharge potential and voltage efficiency, thus holding great promise for achieving a high energy conversion efficiency.

[0162] Electrocatalytic chlorine reduction was tested using commercially available carbon nanotube-supported Pt clusters, RuO2 electrodes, and commercial ruthenium-iridium DSA electrodes. The test conditions were: ambient temperature and pressure, three-electrode system H-type electrode cell, electrolyte saturated with Cl2 in 1M HCl aqueous solution, working electrode was carbon nanotube-supported Pt clusters, RuO2 electrode or commercial ruthenium-iridium DSA electrode, reference electrode was saturated calomel electrode, counter electrode was graphite rod, and ion exchange membrane was Nafion 117 membrane. Figure 18 a represents the electrocatalytic chlorine reduction polarization curves of carbon nanotube-supported Pt clusters, RuO2 electrodes, and commercial ruthenium-iridium DSA electrodes.

[0163] Electrocatalytic hydrogen oxidation was tested using commercially available carbon-supported platinum, carbon-supported iridium, and carbon-supported ruthenium, all sourced from Sigma-Aldrich. The test conditions were: ambient temperature and pressure, rotating disk electrode, electrolyte saturated with H2 in a 0.1M HClO4 aqueous solution, working electrode (carbon-supported platinum, carbon-supported iridium, or carbon-supported ruthenium), reference electrode (saturated calomel electrode), and counter electrode (graphite rod). Figure 18b is the electrocatalytic hydrogen oxidation polarization curve of carbon-supported platinum, carbon-supported iridium, and carbon-supported ruthenium.

[0164] Figure 18 a indicates that chlorine reduction has almost no overpotential and the reversibility of the corresponding chlorine evolution reaction with oxidation is very good. Among the three electrodes, the Pt clusters supported on carbon nanotubes show the best chlorine reduction performance. Figure 18 b indicates that hydrogen oxidation has almost no overpotential and the reversibility of the corresponding reduction hydrogen evolution reaction is very good. Among the three electrodes, carbon-loaded iridium shows the best hydrogen oxidation performance.

[0165] Figure 18 Figures a and b illustrate that the preferred carbon nanotube-supported Pt clusters and carbon-supported platinum can be used as cathode materials in hydrochloric acid electrolysis-based energy cycle systems and anode materials in hydrogen-chlorine fuel cell systems, respectively.

[0166] Small-scale experiment

[0167] (1) Preparation of electrolyte: Concentrated hydrochloric acid was diluted with deionized water to obtain a certain volume of 0.1–10 mol / L. -1 Concentration of dilute hydrochloric acid (10 L in this example, 1 mol L) -1 ), and put it into the hydrochloric acid storage device (1).

[0168] (2) Assembly of the hydrochloric acid hydrogen evolution and chlorine evolution system (2): The self-made titanium-based metal oxide electrode is used as the anode (in this embodiment, the Zr obtained in the following embodiment (2) is used). 0.6 Sb 0.1 Ru 0.3 The cathode is an O2 electrode, and the catalyst is a noble metal catalyst (in this embodiment, it is a Pt cluster supported on carbon nanotubes), with a catalyst loading of 2–10 mg / cm³. -2 (This example uses 5mg cm) -2 The effective active area of ​​each cathode and anode is 25cm². 2 It is assembled with other components to form a film electrode, and is also equipped with a temperature and pressure detection device to monitor the temperature and pressure of the system in real time.

[0169] (3) A corrosion-resistant chemical-grade liquid pump is used to transport the dilute hydrochloric acid of a certain concentration prepared in step (1) into the electrolytic hydrochloric acid hydrogen and chlorine evolution system (2) (in this embodiment, it is 1 mol L). -1 (Speed ​​100L / h).

[0170] (4) Intermittently renewable electrical energy is connected to the electrolytic hydrochloric acid hydrogen and chlorine evolution system (2) assembled in step (2). The operating conditions are ambient temperature and pressure, constant current electrolysis mode, and electrolysis at an electrolysis rate of 50-750 mA (250 mA in this embodiment), corresponding to a voltage of (1.36-1.52 V) (1.41 V in this embodiment). The generated chlorine and hydrogen are sequentially passed through a gas-liquid separator, dehydrated by a condenser, and dehydrated by 3-10 concentrated sulfuric acid wash bottles (5 in this embodiment), before passing through a chlorine and hydrogen collection device. The rate at which hydrogen and chlorine are generated at the anode and cathode is approximately 30-110 mL / min (70 mL / min in this embodiment).

[0171] (5) The chlorine and hydrogen collected in step (4) above are pressurized to 1.8 to 2.2 MPa by a gas compression and pressurization device and then sent to a chlorine and hydrogen storage device (2.0 MPa in this embodiment). The gas pressure of the storage device is 1.2 to 1.5 MPa (1.5 MPa in this embodiment).

[0172] (6) Hydrogen-chlorine fuel cell (7) Assembly: using commercially available carbon-supported platinum as the cathode catalyst for chlorine reduction and the anode catalyst for hydrogen oxidation (source: Sigma-Aldrich), with a catalyst loading of 2–10 mg / cm³. -2 (This example uses 5mgcm) -2 The effective active area of ​​each cathode and anode is 25cm². 2 It is assembled with other components into a film electrode assembly, and a temperature and pressure detection device is also installed to monitor the temperature and pressure of the system in real time.

[0173] (7) When the hydrogen-chlorine fuel cell (7) needs to be discharged, the chlorine and hydrogen storage tanks in step (5) are used as fuel. The flow rate is controlled by a corrosion-resistant chemical special gas flow meter and is directed to five washing bottles containing deionized water at a rate of 30-110 mL / min to fully contact and wet the water (70 mL / min in this embodiment). Then, the gas is directed to the hydrogen-chlorine fuel cell for discharge at a current of 50-750 mA (250 mA in this embodiment), with a discharge voltage of 1.36-1.30 (1.33 V in this embodiment) and a corresponding power of 332.5 mW.

[0174] (8) The hydrogen chloride generated at the cathode in step (7) above is fed to the hydrogen chloride-hydrogen separation device (8), where it is absorbed by 3 to 10 saturated brine washing bottles (5 in this embodiment), and the remaining chlorine is recycled back to the chlorine storage device (6).

[0175] (9) The saturated brine from which hydrogen chloride was dissolved in step (8) is fed to the hydrochloric acid recovery and purification device (9) to purify hydrogen chloride by distillation. The evaporation temperature is 80-85℃ (85℃ in this embodiment).

[0176] (10) The purified hydrogen chloride from step (9) is recycled back to the hydrochloric acid storage device (1) in step (1) through the hydrogen chloride reflux pipe 115, realizing the recycling of materials and energy. The remaining saturated brine is recycled back to the hydrogen chloride hydrogen separation device (8) through the saturated brine reflux pipe (114).

[0177] Example 1

[0178] Preparation of a low-noble metal mixed oxide electrode for electrocatalytic chloride ion oxidation.

[0179] This embodiment provides Zr x Sb y Ru 1-x-y The preparation method of the O2 electrode includes the following steps, which can be adjusted by those skilled in the art with reference to existing technology:

[0180] (1) Prepare alcohol solutions of the metals respectively.

[0181] (2) The alcohol solutions prepared in step (1) are mixed according to different molar ratios to obtain uniformly dispersed solutions; then a polymer with multidentate ligands is added to the solution, and the mixture is heated and stirred to allow it to react fully.

[0182] (3) The solution obtained in step (2) is uniformly brushed onto the porous conductive substrate and then heated and dried. In this embodiment, the porous conductive substrate is titanium felt. The coating-heating and drying process is performed a total of 3 times.

[0183] (4) The porous conductive substrate was then placed in a muffle furnace for calcination, allowing it to fully contact and react with air, and then cooled to room temperature in air. This calcination-cooling process was performed a total of 3 times.

[0184] (5) The porous conductive substrate was then placed in a muffle furnace for calcination, allowing it to fully contact and react with air, thus ensuring a tight bond between the porous conductive substrate and the catalyst on its surface. The substrate was then cooled to room temperature in the furnace to obtain Zr. x Sb y Ru 1-x-y O2 electrode. This embodiment specifically obtains Zr. 0.6 Sb 0.1 Ru 0.3 O2 electrode.

[0185] In step (1), the alcoholic solution of the metal is an alcoholic solution of ruthenium trichloride, zirconium butoxide, and antimony trichloride, each with a concentration of 0.5 mol / L. -1 ~1mol L -1 In this embodiment, all concentrations are 0.5 mol / L. -1 .

[0186] The mixed solution mentioned in step (2) is an alcoholic solution of ruthenium trichloride, zirconium butoxide, and antimony trichloride; the total amount of metal in the mixed solution is 0.5-2 mmol, and in this example, it is 2 mmol. The molar ratio of ruthenium, zirconium, and antimony in the mixed solution is 3:6:1. The amount of polymer with polydentate ligands added is 60-240 mg, and in this example, 240 mg of polyvinyl alcohol is added. The heating and stirring temperature is 50-90℃, and the time is 2-8 h, and in this example, stirring is carried out at 50℃ for 8 h.

[0187] The drying temperature in step (3) is 50–90°C, and in this embodiment it is 90°C. The drying time is 1–20 min, and in this embodiment it is 1 min.

[0188] The calcination temperature in the muffle furnace in step (4) is 400-600℃, and in this embodiment it is 600℃. The calcination time is 1-20 min, and in this embodiment it is 1 min.

[0189] The muffle furnace temperature in step (5) is 400-600℃, and in this embodiment it is 600℃. The calcination time is 0.5-3h, and in this embodiment it is 0.5h. The loading of mixed metal oxides on the conductive substrate surface is 1-20mg / cm³. -2 The load thickness is 1-100 μm. In this embodiment, the load is 1 mg / cm³. -2 The load thickness is 1μm.

[0190] The electrode Zr obtained above 0.6 Sb 0.1 Ru 0.3 O2 can be used directly as a working electrode without further processing.

[0191] Comparative Example 1

[0192] The preparation method is the same as in Example 1, except that the molar ratio of ruthenium, zirconium, and antimony in the mixed solution is 2:7:1. The resulting electrode is Zr. 0.7 Sb 0.1 Ru 0.2 O2.

[0193] Example 2

[0194] The preparation method is the same as in Example 1, except that the molar ratio of zirconium, antimony, and ruthenium in the mixed solution is 1:1:8. Furthermore, the porous conductive substrate is a titanium mesh.

[0195] The electrode prepared is Zr 0.1 Sb 0.1 Ru 0.8 O2.

[0196] Comparative Example 2

[0197] The preparation method is the same as in Example 2, except that the molar ratio of zirconium, antimony, and ruthenium in the mixed solution is 5:5:90. The resulting electrode is Zr. 0.05 Sb 0.05 Ru 0.9 O2.

[0198] Example 3

[0199] This embodiment provides Zr x V y Ru 1-x-y The preparation method of the O2 electrode includes the following steps, referring to the preparation method in Example 1.

[0200] In step (1), the alcoholic solution of the metal is an alcoholic solution of ruthenium trichloride, zirconium butoxide, and vanadium trichloride, with a concentration of 0.5 mol / L. -1 ~1mol L -1 In this embodiment, all concentrations are 0.5 mol / L. -1 .

[0201] The mixed solution mentioned in step (2) is an alcoholic solution of ruthenium trichloride, zirconium butoxide, and vanadium trichloride; the total amount of metal in the mixed solution is 0.5-2 mmol, and in this embodiment, it is 2 mmol. The molar ratio of ruthenium, zirconium, and vanadium in the mixed solution is 3:6:1. The amount of polymer with multidentate ligands added is 60-240 mg, and in this embodiment, 240 mg of polyethylene glycol is added. The heating and stirring temperature is 50-90℃, and the time is 2-8 h, and in this embodiment, stirring is carried out at 80℃ for 4 h. The porous conductive substrate is carbon paper.

[0202] The drying temperature in step (3) is 50–90°C, and in this embodiment it is 80°C. The drying time is 1–20 min, and in this embodiment it is 5 min.

[0203] The calcination temperature in the muffle furnace in step (4) is 400-600℃, and in this embodiment it is 500℃. The calcination time is 1-20 min, and in this embodiment it is 5 min.

[0204] The muffle furnace temperature in step (5) is 400-600℃, and in this embodiment it is 500℃. The calcination time is 0.5-3h, and in this embodiment it is 1h. The loading of mixed metal oxides on the conductive substrate surface is 1-20mg / cm³. -2 The load thickness is 1-100 μm. In this embodiment, the load is 4.2 mg / cm³. -2 The load thickness is 37μm.

[0205] The electrode Zr obtained above 0.6 V0.1 Ru 0.3 O2 can be used directly as a working electrode without further processing.

[0206] Comparative Example 3

[0207] The preparation method is the same as in Example 3, except that the molar ratio of zirconium, vanadium, and ruthenium in the mixed solution is 7:1:2. The resulting electrode is Zr. 0.7 V 0.1 Ru 0.2 O2.

[0208] Example 4

[0209] The preparation method is the same as in Example 3, except that the molar ratios of zirconium, vanadium, and ruthenium in the mixed solution are 1:1:8. Furthermore, the porous conductive substrate is carbon cloth.

[0210] The electrode prepared is Zr 0.1 V 0.1 Ru 0.8 O2.

[0211] Comparative Example 4

[0212] The preparation method is the same as in Example 4, except that the molar ratio of zirconium, vanadium, and ruthenium in the mixed solution is 5:5:90. The resulting electrode is Zr. 0.05 V 0.05 Ru 0.9 O2.

[0213] Example 5

[0214] Preparation of a low-noble metal mixed oxide electrode for electrocatalytic chloride ion oxidation.

[0215] This embodiment provides Sn x Nb y Ru 1-x-y The preparation method of the O2 electrode includes the following steps, referring to the preparation method in Example 1.

[0216] The alcoholic solution of the metal mentioned in step (1) is an alcoholic solution of ruthenium trichloride, tin tetrachloride, and niobium pentachloride, each with a concentration of 0.5 mol / L. -1 ~1mol L -1 In this embodiment, all concentrations are 0.5 mol / L. -1 .

[0217] The mixed solution mentioned in step (2) is an alcoholic solution of ruthenium trichloride, tin tetrachloride, and niobium pentachloride; the total amount of metal in the mixed solution is 2 mmol, and the molar ratio of ruthenium, tin, and niobium in the mixed solution is 3:6:1. The amount of polymer with polydentate ligands added is 60-240 mg, and in this example, 240 mg of polyethylene glycol is added. The heating and stirring temperature is 50-90℃, and the time is 2-8 h, and in this example, stirring is carried out at 60℃ for 6 h.

[0218] The drying temperature in step (3) is 50–90°C, and in this embodiment it is 60°C. The drying time is 1–20 min, and in this embodiment it is 10 min.

[0219] The calcination temperature in the muffle furnace in step (4) is 400-600℃, and in this embodiment it is 450℃. The calcination time is 1-20 min, and in this embodiment it is 10 min.

[0220] The muffle furnace temperature in step (5) is 400-600℃, and in this embodiment it is 450℃. The calcination time is 0.5-3h, and in this embodiment it is 2h. The loading of mixed metal oxides on the conductive substrate surface is 1-20mg / cm³. -2 The load thickness is 1-100 μm. In this embodiment, the load is 3.8 mg / cm³. -2 The load thickness is 35μm.

[0221] The electrode Sn obtained above 0.6 Nb 0.1 Ru 0.3 O2 can be used directly as a working electrode without further processing.

[0222] Comparative Example 5

[0223] The preparation method is the same as in Example 5, except that the molar ratio of tin, niobium, and ruthenium in the mixed solution is 7:1:2. The resulting electrode is Sn. 0.7 Nb 0.1 Ru 0.2 O2.

[0224] Example 6

[0225] The preparation method is the same as in Example 5, except that the molar ratio of tin, niobium, and ruthenium in the mixed solution is 1:1:8. The resulting electrode is Sn. 0.1 Nb 0.1 Ru 0.8 O2.

[0226] Comparative Example 6

[0227] The preparation method is the same as in Example 5, except that the molar ratio of tin, niobium, and ruthenium in the mixed solution is 5:5:90. The resulting electrode is Sn. 0.05 Nb 0.05 Ru 0.9 O2.

[0228] Example 7

[0229] Preparation of a low-noble metal mixed oxide electrode for electrocatalytic chloride ion oxidation.

[0230] This embodiment provides Sn x Ti y Ru 1-x-y The preparation method of the O2 electrode includes the following steps, referring to the preparation method in Example 1.

[0231] The alcoholic solution of the metal mentioned in step (1) is an alcoholic solution of ruthenium trichloride, tin tetrachloride, and tetrabutyl titanate, with a concentration of 0.5 mol / L. -1 ~1mol L -1 In this embodiment, all values ​​are 1 mol L. -1 .

[0232] The mixed solution mentioned in step (2) is an alcoholic solution of ruthenium trichloride, tin tetrachloride, and tetrabutyl titanate; the total amount of metal in the mixed solution is 0.5 mmol, and the molar ratio of ruthenium, tin, and titanium in the mixed solution is 3:6:1. The amount of polymer with multidentate ligands added is 60-240 mg; in this example, 60 mg of polyvinylpyrrolidone is added. The heating and stirring temperature is 50-90℃, and the time is 2-8 h; in this example, stirring is carried out at 90℃ for 2 h.

[0233] The drying temperature in step (3) is 50–90°C, and in this embodiment it is 50°C. The drying time is 1–20 min, and in this embodiment it is 20 min.

[0234] The calcination temperature in the muffle furnace in step (4) is 400-600℃, and in this embodiment it is 400℃. The calcination time is 1-20 min, and in this embodiment it is 20 min.

[0235] The muffle furnace temperature in step (5) is 400-600℃, and in this embodiment it is 400℃. The calcination time is 0.5-3h, and in this embodiment it is 3h. The loading of mixed metal oxides on the conductive substrate surface is 1-20mg / cm³. -2 The load thickness is 1-100 μm. In this embodiment, the load is 20 mg / cm³. -2 The load thickness is 100μm.

[0236] The electrode Sn obtained above 0.6 Ti0.1 Ru 0.3 O2 can be used directly as a working electrode without further processing.

[0237] Comparative Example 7

[0238] The preparation method described in Example 7 differs from that in Example 7 only in that the molar ratio of tin, titanium, and ruthenium in the mixed solution is 7:1:2. The resulting electrode is Sn. 0.7 Ti 0.1 Ru 0.2 O2.

[0239] Example 8

[0240] The preparation method is the same as in Example 7, except that the molar ratio of tin, titanium, and ruthenium in the mixed solution is 1:1:8. The resulting electrode is Sn. 0.1 Ti 0.1 Ru 0.8 O2.

[0241] Comparative Example 8

[0242] The preparation method is the same as in Example 8, except that the molar ratio of tin, titanium, and ruthenium in the mixed solution is 5:5:90. The resulting electrode is Sn. 0.05 Ti 0.05 Ru 0.9 O2.

[0243] Example 9

[0244] Preparation of a low-noble metal mixed oxide electrode for electrocatalytic chloride ion oxidation.

[0245] This embodiment provides Ti x Sn y Sb z Ru 1-x-y-z The preparation method of the O2 electrode includes the following steps, referring to the preparation method in Example 1.

[0246] The alcoholic solution of the metal mentioned in step (1) is an alcoholic solution of tetrabutyl titanate, tin tetrachloride, antimony trichloride, and ruthenium trichloride, with a concentration of 0.5 mol / L. -1 ~1mol L -1 In this embodiment, all values ​​are 1 mol L. -1 .

[0247] The mixed solution mentioned in step (2) is an alcoholic solution of tetrabutyl titanate, tin tetrachloride, antimony trichloride, and ruthenium trichloride; the total amount of metal in the mixed solution is 0.5 mmol, and the molar ratio of ruthenium, titanium, tin, and antimony in the mixed solution is 3:2:2:3. The amount of polymer with multidentate ligands added is 60-240 mg, and in this example, 120 mg of polyvinylpyrrolidone is added. The heating and stirring temperature is 50-90℃, and the time is 2-8 h, and in this example, stirring is carried out at 80℃ for 2 h.

[0248] The drying temperature in step (3) is 50–90°C, and in this embodiment it is 60°C. The drying time is 1–20 min, and in this embodiment it is 10 min.

[0249] The calcination temperature in the muffle furnace in step (4) is 400-600℃, and in this embodiment it is 450℃. The calcination time is 1-20 min, and in this embodiment it is 10 min.

[0250] The muffle furnace temperature in step (5) is 400-600℃, and in this embodiment it is 450℃. The calcination time is 0.5-3h, and in this embodiment it is 2h. The loading of mixed metal oxides on the conductive substrate surface is 1-20mg / cm³. -2 The load thickness is 1-100 μm. In this embodiment, the load is 15 mg / cm³. -2 The load thickness is 80μm.

[0251] The electrode Ti obtained above 0.2 Sn 0.2 Sb 0.3 Ru 0.3 O2 can be used directly as a working electrode without further processing.

[0252] Example 10

[0253] Preparation of a low-noble metal mixed oxide electrode for electrocatalytic chloride ion oxidation.

[0254] This embodiment provides Nb x Zr y V z Ru 1-x-y-z The preparation method of the O2 electrode includes the following steps, referring to the preparation method in Example 1.

[0255] The alcoholic solution of the metal mentioned in step (1) is an alcoholic solution of niobium pentachloride, zirconium tetrachloride, vanadium trichloride, and ruthenium trichloride, with a concentration of 0.5 mol / L. -1 ~1mol L -1 In this embodiment, all values ​​are 1 mol L. -1 .

[0256] The mixed solution mentioned in step (2) is an alcoholic solution of niobium pentachloride, zirconium tetrachloride, vanadium trichloride, and ruthenium trichloride; the total amount of metal in the mixed solution is 0.5 mmol, and the molar ratio of ruthenium, niobium, zirconium, and vanadium in the mixed solution is 3:2:2:3. The amount of polymer with polydentate ligands added is 60-240 mg, and in this example, 150 mg of polyvinylpyrrolidone is added. The heating and stirring temperature is 50-90℃, and the time is 2-8 h, and in this example, stirring is carried out at 70℃ for 5 h.

[0257] The drying temperature in step (3) is 50–90°C, and in this embodiment it is 70°C. The drying time is 1–20 min, and in this embodiment it is 10 min.

[0258] The calcination temperature in the muffle furnace in step (4) is 400-600℃, and in this embodiment it is 450℃. The calcination time is 1-20 min, and in this embodiment it is 10 min.

[0259] The muffle furnace temperature in step (5) is 400-600℃, and in this embodiment it is 450℃. The calcination time is 0.5-3h, and in this embodiment it is 2h. The loading of mixed metal oxides on the conductive substrate surface is 1-20mg / cm³. -2 The load thickness is 1-100 μm. In this embodiment, the load is 12 mg / cm³. -2 The load thickness is 70μm.

[0260] The electrode Nb obtained above 0.2 Zr 0.2 V 0.3 Ru 0.3 O2 can be used directly as a working electrode without further processing.

[0261] Example 11

[0262] Preparation of a low-noble metal mixed oxide electrode for electrocatalytic chloride ion oxidation.

[0263] This embodiment provides Co x Fe y Ni z Ru 1-x-y-z The preparation method of the O2 electrode includes the following steps, referring to the preparation method in Example 1.

[0264] The alcoholic solution of the metal mentioned in step (1) is an alcoholic solution of cobalt trichloride, ferric trichloride, nickel chloride, and ruthenium trichloride, with a concentration of 0.5 mol / L. -1 ~1mol L -1 In this embodiment, all values ​​are 1 mol L. -1 .

[0265] The mixed solution mentioned in step (2) is an alcoholic solution of cobalt trichloride, ferric trichloride, vanadium trichloride, and nickel chloride; the total amount of metal in the mixed solution is 0.5 mmol, and the molar ratio of ruthenium, niobium, zirconium, and vanadium in the mixed solution is 7:1:1:1. The amount of polymer with polydentate ligands added is 60-240 mg, and in this example, 150 mg of polyvinylpyrrolidone is added. The heating and stirring temperature is 50-90℃, and the time is 2-8 h, and in this example, stirring is carried out at 80℃ for 5 h.

[0266] The drying temperature in step (3) is 50–90°C, and in this embodiment it is 70°C. The drying time is 1–20 min, and in this embodiment it is 10 min.

[0267] The calcination temperature in the muffle furnace in step (4) is 400-600℃, and in this embodiment it is 450℃. The calcination time is 1-20 min, and in this embodiment it is 10 min.

[0268] The temperature of the muffle furnace in step (5) is 400-600℃, and in this embodiment it is 450℃. The calcination time is 0.5-3 hours, and in this embodiment it is 2 hours. Co x Fe y Ni z Ru 1-x-y-z In the O2 electrode, the loading of mixed metal oxides on the conductive substrate surface is 1-20 mg / cm³. -2 The load thickness is 1-100 μm. In this embodiment, the load is 12 mg / cm³. -2 The load thickness is 70μm.

[0269] The electrode Co obtained above 0.1 Fe 0.1 Ni 0.1 Ru 0.7 O2 can be used directly as a working electrode without further processing.

[0270] Example 12

[0271] Preparation of a low-noble metal mixed oxide electrode for electrocatalytic chloride ion oxidation.

[0272] This embodiment provides Ti a Sn b Sb c Nb d Zr e V f Co g Fe h Ni i Ru j The preparation method of the O2 electrode includes the following steps, referring to the preparation method in Example 1.

[0273] The alcoholic solution of the metal mentioned in step (1) is an alcoholic solution of tetrabutyl titanate, tin tetrachloride, antimony trichloride, niobium pentachloride, zirconium tetrachloride, vanadium trichloride, cobalt trichloride, ferric chloride, nickel chloride, and ruthenium trichloride, with a concentration of 0.5 mol / L. -1 ~1mol / L -1 In this embodiment, all values ​​are 1 mol L. -1 .

[0274] The mixed solution mentioned in step (2) is an alcoholic solution of tetrabutyl titanate, tin tetrachloride, antimony trichloride, niobium pentachloride, zirconium tetrachloride, vanadium trichloride, cobalt trichloride, ferric chloride, nickel chloride, and ruthenium trichloride; the total amount of metal in the mixed solution is 0.5 mmol, and the molar ratio of titanium, tin, antimony, niobium, zirconium, vanadium, cobalt, iron, nickel, and ruthenium in the mixed solution is 14:7:7:7:7:7:7:7:7:30. The amount of polymer with multidentate ligands added is 60-240 mg, and in this example, 150 mg of polyvinylpyrrolidone is added. The heating and stirring temperature is 50-90℃, and the time is 2-8 h, and in this example, stirring is carried out at 80℃ for 4 h.

[0275] The drying temperature in step (3) is 50–90°C, and in this embodiment it is 70°C. The drying time is 1–20 min, and in this embodiment it is 10 min.

[0276] The calcination temperature in the muffle furnace in step (4) is 400-600℃, and in this embodiment it is 450℃. The calcination time is 1-20 min, and in this embodiment it is 10 min.

[0277] The muffle furnace temperature in step (5) is 400-600℃, and in this embodiment it is 450℃. The calcination time is 0.5-3 hours, and in this embodiment it is 2 hours. The loading of mixed metal oxides on the conductive substrate surface is 1-20 mg / cm³. -2 The load thickness is 1-100 μm. In this embodiment, the load is 10 mg / cm³. -2 The load thickness is 60μm.

[0278] The electrode Ti obtained above 0.14 Sn 0.07 Sb 0.07 Nb 0.07 Zr 0.07 V 0.07 Co 0.07 Fe 0.07 Ni 0.07 Ru 0.3 O2 can be used directly as a working electrode without further processing.

[0279] Morphological characteristics:

[0280] Morphological characterization of the low-noble metal mixed oxide electrode obtained above.

[0281] The electrodes obtained in Examples 1, 3, 5, and 7 were subjected to scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) tests. Figure 1 In the equation, a, b, c, and d represent Zr values ​​respectively. 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru 0.3 O2, Sn 0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 The SEM images of the O2 electrodes show that the surfaces of all four electrodes exhibit uniform mud-crack patterns, which is typical of sintered oxide electrodes. Figure 2 , 3 Zr, 4, and 5 respectively 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru 0.3 O2, Sn 0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 The surface elemental distribution diagram of the O2 electrode shows that the metal elements in the prepared mixed metal oxide are uniformly dispersed.

[0282] For Zr respectively 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru 0.3 O2, Sn 0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 The O2 electrode was subjected to ultrasonication and centrifugal drying in an alcohol solution to obtain its surface particles, which were then analyzed by transmission electron microscopy (TEM). The results are as follows: Figure 6 As shown, where a, b, c, and d are Zr values ​​respectively. 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru0.3 O2, Sn 0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 The TEM image corresponding to the O2 electrode shows that the surface of the fabricated mixed metal oxide electrode is composed of nanoparticles with a size of 5 to 100 nanometers.

[0283] Application Example 1

[0284] Electrochemical performance and chlorine selectivity of the low-noble-metal mixed oxide electrode used for electrocatalytic chloride ion oxidation in hydrochloric acid.

[0285] The electrodes obtained in Examples 1, 3, 5, 7, 9, 10, 11, and 12 were subjected to performance and selectivity tests for electrocatalytic chlorine production under acidic conditions.

[0286] The testing method is as follows:

[0287] At room temperature, a two-chamber H-type electrolytic cell with a diaphragm was connected to an electrochemical workstation for testing. The diaphragm was a Nation 117 proton exchange membrane. Each chamber of the electrolytic cell had a capacity of 50 mL. An Ag / AgCl electrode was used as the reference electrode, and a platinum sheet was used as the counter electrode. The prepared electrode and a commercial ruthenium-iridium DSA electrode were used as the working electrodes. 40 mL of 1 mol L⁻¹ solution was added to each side of the electrolytic cell. -1 A hydrochloric acid solution (pH=0) was used as the electrolyte. The performance of the electrocatalytic chlorine production was tested using a linear sweep voltammetry system. The chlorine content obtained from the electrolysis of the hydrochloric acid solution was measured by iodometric titration and compared with the theoretical value to obtain the chlorine selectivity.

[0288] Figure 7 The nine curves A, B, C, D, E, F, G, H, and I represent Zr... 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru 0.3 O2, Sn 0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 O2, Ti 0.2 Sn 0.2 Sb 0.3 Ru 0.3 O2, Nb 0.2 Zr 0.2 V 0.3 Ru 0.3 O2, Co0.1 Fe 0.1 Ni 0.1 Ru 0.7 O2, Ti 0.14 Sn 0.07 Sb 0.07 Nb 0.07 Zr 0.07 V 0.07 Co 0.07 Fe 0.07 Ni 0.07 Ru 0.3 Polarization curves of the O2 electrode and the commercial ruthenium-iridium DSA electrode are shown. It can be seen that the overpotentials at a current density of 10 mA / cm² are 43 mV, 50 mV, 45 mV, 53 mV, 51 mV, 48 mV, 55 mV, and 56 mV, respectively, all lower than the 60 mV of the commercial ruthenium-iridium DSA electrode. This indicates that the electrodes obtained in Examples 1, 3, 5, 7, 9, 10, 11, and 12 all exhibit better electrochemical activity than the commercial ruthenium-iridium DSA electrode.

[0289] Figure 8 A, B, C, D, E, F, G, H, and I represent Zr... 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru 0.3 O2, Sn 0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 O2, Ti 0.2 Sn 0.2 Sb 0.3 Ru 0.3 O2, Nb 0.2 Zr 0.2 V 0.3 Ru 0.3 O2, Co 0.1 Fe 0.1 Ni 0.1 Ru 0.7 O2, Ti 0.14 Sn 0.07 Sb 0.07 Nb 0.07 Zr 0.07 V 0.07 Co 0.07 Fe 0.07 Ni 0.07 Ru 0.3 Chlorine selectivity histograms for O2 electrode and commercial ruthenium-iridium DSA electrode, where Zr 0.6 Sb0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru 0.3 O2, Sn 0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 O2, Ti 0.2 Sn 0.2 Sb 0.3 Ru 0.3 O2, Nb 0.2 Zr 0.2 V 0.3 Ru 0.3 O2, Co 0.1 Fe 0.1 Ni 0.1 Ru 0.7 O2, Ti 0.14 Sn 0.07 Sb 0.07 Nb 0.07 Zr 0.07 V 0.07 Co 0.07 Fe 0.07 Ni 0.07 Ru 0.3 The selectivity of the O2 electrode for chlorine production was 94.0%, 93.3%, 92.4%, 93.7%, 93.6%, 90.6%, 89.3%, and 88.7%, respectively, all higher than the 87.4% of the commercial ruthenium-iridium DSA electrode. This indicates that the electrodes obtained in Examples 1, 3, 5, 7, 9, 10, 11, and 12 all have higher chlorine selectivity than the commercial ruthenium-iridium DSA electrode.

[0290] The above tests fully demonstrate that the low-noble metal mixed oxide electrode obtained by the sol-gel method has better electrochemical performance and higher chlorine selectivity than the commercial ruthenium-iridium DSA electrode.

[0291] Application Example 2

[0292] The electrodes obtained in Examples 1, 2, Comparative Example 1, and 2, as well as the commercial ruthenium-iridium DSA electrode, were subjected to electrocatalytic chlorine production performance tests, using the same methods as in Application Example 1.

[0293] The obtained polarization curves are as follows Figure 9 As shown, curves A, B, C, D, and E represent the Zr values ​​obtained in Example 1. 0.6 Sb 0.1 Ru 0.3 O2 electrode, Zr obtained in Example 2 0.1 Sb 0.1Ru 0.8 O2 electrode, Zr obtained from Comparative Example 1 0.7 Sb 0.1 Ru 0.2 O2 electrode, Zr obtained from Comparative Example 2 0.05 Sb 0.05 Ru 0.9 Polarization curves of O2 electrode and commercial ruthenium-iridium DSA electrode.

[0294] It can be seen that the performance of the electrodes obtained in Examples 1 and 2 in producing chlorine gas by electrocatalysis is better than that of the commercial ruthenium-iridium DSA electrode.

[0295] The electrocatalytic chlorine production performance of the electrodes obtained in Comparative Examples 1 and 2 was significantly worse than that of the electrodes obtained in Examples 1 and 2 and the commercial ruthenium-iridium DSA electrode. At a current density of 10 mA / cm², the overpotentials were 84 mV and 65 mV, respectively, which were much greater than those of the electrodes obtained in Examples 1 and 2 (overpotentials of 43 mV and 52 mV) and the commercial ruthenium-iridium DSA electrode (overpotential of 60 mV).

[0296] Application Example 3

[0297] The electrodes obtained in Examples 3, 4, Comparative Examples 3 and 4, as well as the commercial ruthenium-iridium DSA electrode, were subjected to electrocatalytic chlorine production performance tests, using the same methods as in Application Example 1.

[0298] The obtained polarization curves are as follows Figure 10 As shown, curves A, B, C, D, and E represent the Zr values ​​obtained in Example 3. 0.6 Sb 0.1 Ru 0.3 O2 electrode, Zr obtained in Example 4 0.1 V 0.1 Ru 0.8 O2 electrode, Zr obtained from Comparative Example 3 0.7 V 0.1 Ru 0.2 O2 electrode, Zr obtained from Comparative Example 4 0.05 V 0.05 Ru 0.9 Polarization curves of O2 electrode and commercial ruthenium-iridium DSA electrode.

[0299] It can be seen that the performance of the electrodes obtained in Examples 3 and 4 in producing chlorine gas by electrocatalysis is better than that of commercial ruthenium-iridium DSA electrodes.

[0300] The electrocatalytic chlorine production performance of the electrodes obtained in Comparative Examples 3 and 4 was significantly worse than that of the electrodes obtained in Examples 3 and 4 and the commercial ruthenium-iridium DSA electrode. At a current density of 10 mA / cm², the overpotentials were 108 mV and 76 mV, respectively, which were much greater than those of the electrodes obtained in Examples 3 and 4 (overpotentials of 50 mV and 49 mV) and the commercial ruthenium-iridium DSA electrode (overpotential of 60 mV).

[0301] Application Example 4

[0302] The electrodes obtained in Examples 5, 6, Comparative Examples 5 and 6, as well as the commercial ruthenium-iridium DSA electrode, were subjected to electrocatalytic chlorine production performance tests, using the same methods as in Application Example 1.

[0303] The obtained polarization curves are as follows Figure 11 As shown, curves A, B, C, D, and E represent the Sn obtained in Example 5. 0.6 Nb 0.1 Ru 0.3 O2 electrode, Sn obtained in Example 6 0.1 Nb 0.1 Ru 0.8 O2 electrode, Sn obtained from Comparative Example 5 0.7 Nb 0.1 Ru 0.2 O2 electrode, Sn obtained from Comparative Example 6 0.05 Nb 0.05 Ru 0.9 Polarization curves of O2 electrode and commercial ruthenium-iridium DSA electrode.

[0304] It can be seen that the performance of the electrodes obtained in Examples 5 and 6 in electrocatalytic chlorine production is better than that of commercial ruthenium-iridium DSA electrodes.

[0305] The electrocatalytic chlorine production performance of the electrodes obtained in Comparative Examples 5 and 6 was significantly worse than that of the electrodes obtained in Examples 5 and 6 and the commercial ruthenium-iridium DSA electrode. The overpotentials at a current density of 10 mA / cm² were 90 mV and 63 mV, respectively, which were much greater than those of the electrodes obtained in Examples 5 and 6 (45 mV and 48 mV) and the commercial ruthenium-iridium DSA electrode (60 mV).

[0306] Application Example 5

[0307] The electrodes obtained in Examples 7, 8, Comparative Examples 7 and 8, as well as the commercial ruthenium-iridium DSA electrode, were subjected to electrocatalytic chlorine production performance tests, using the same methods as in Application Example 1.

[0308] The obtained polarization curves are as follows Figure 12 As shown, curves A, B, C, D, and E represent the Sn obtained in Example 7. 0.6 Ti 0.1 Ru0.3 O2 electrode, Sn obtained in Example 8 0.1 Ti 0.1 Ru 0.8 O2 electrode, Sn obtained from Comparative Example 7 0.7 Ti 0.1 Ru 0.2 O2 electrode, Sn obtained from Comparative Example 8 0.05 Ti 0.05 Ru 0.9 Polarization curves of O2 electrode and commercial ruthenium-iridium DSA electrode.

[0309] It can be seen that the performance of the electrodes obtained in Examples 7 and 8 in producing chlorine gas by electrocatalysis is better than that of commercial ruthenium-iridium DSA electrodes.

[0310] The electrocatalytic chlorine production performance of the electrodes obtained in Comparative Examples 7 and 8 was significantly worse than that of the electrodes obtained in Examples 7 and 8 and the commercial ruthenium-iridium DSA electrode. The overpotentials at a current density of 10 mA / cm² were 106 mV and 67 mV, respectively, which were much greater than those of the electrodes obtained in Examples 7 and 8 (53 mV and 54 mV) and the commercial ruthenium-iridium DSA electrode (60 mV).

[0311] As can be seen from application examples 2-5, too much or too little element doping does not achieve the desired effect: with less element doping (i.e., x < 20%), the change in the performance of the ruthenium dioxide electrode is not obvious, and its preparation cost is not significantly reduced, so its practical application value is not great; with more element doping (i.e., x > 70%), due to the excessive proportion of doped metal, the original crystal structure of ruthenium dioxide is greatly distorted, which leads to changes in the electrode structure and a sharp decline in electrode performance, which is lower than that of commercial ruthenium-iridium DSA electrodes.

[0312] Application Example 6

[0313] Electrochemical stability test of a low-noble-metal mixed oxide electrode used for electrocatalytic chloride ion oxidation.

[0314] The stability of the electrodes obtained in Examples 1, 3, 5, and 7 for electrocatalytic chlorine production was tested.

[0315] The testing method is as follows:

[0316] At room temperature, a two-chamber H-type electrolytic cell with a diaphragm was connected to an electrochemical workstation for testing. The diaphragm was a Nation 117 proton exchange membrane. Each chamber of the electrolytic cell had a capacity of 50 mL. An Ag / AgCl electrode was used as the reference electrode, and a platinum sheet was used as the counter electrode. The prepared electrode and a commercial ruthenium-iridium DSA electrode were used as the working electrodes. 40 mL of 1 mol L⁻¹ solution was added to each side of the electrolytic cell. -1A hydrochloric acid solution was used as the electrolyte and replenished periodically. The stability of the electrocatalytic chlorine production was tested using a constant current testing system.

[0317] Figure 13 A, B, C, D, and E represent Zr, respectively. 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru 0.3 O2, Sn 0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 The stability test results of the electrocatalytic chlorine production of the O2 electrode and the commercial ruthenium-iridium DSA electrode show that the electrodes obtained in Examples 1, 3, 5, and 7 require voltages of 1.44, 1.45, 1.45, and 1.47 volts (relative to the standard hydrogen electrode) to reach the same current density (100 mA / cm²), respectively. These voltages are lower than those of the commercial ruthenium-iridium DSA electrode (1.49 volts, relative to the standard hydrogen electrode). All of them can operate stably for 500 hours at a current density of 100 mA / cm² without a significant increase in voltage.

[0318] This indicates that the low-noble metal mixed oxide electrode obtained by the sol-gel method has excellent electrochemical stability comparable to that of commercial ruthenium-iridium DSA electrodes.

[0319] Application Example 7

[0320] Electrochemical performance test of a low-noble-metal mixed oxide electrode used for electrocatalytic chloride ion oxidation in neutral saline solution.

[0321] The electrodes obtained in Examples 1, 3, 5, 7, 9, 10, 11, and 12, and a commercial ruthenium-iridium DSA electrode were tested for their electrocatalytic production of hypochlorous acid under neutral conditions.

[0322] The test method is the same as in Application Example 1, except that the electrolyte is 1 mol L. -1 A sodium chloride solution (pH=7) was used as the electrolyte.

[0323] Figure 14 A, B, C, D, E, F, G, H, and I represent Zr... 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru 0.3 O2, Sn 0.6 Nb 0.1 Ru0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 O2, Ti 0.2 Sn 0.2 Sb 0.3 Ru 0.3 O2, Nb 0.2 Zr 0.2 V 0.3 Ru 0.3 O2, Co 0.1 Fe 0.1 Ni 0.1 Ru 0.7 O2, Ti 0.14 Sn 0.07 Sb 0.07 Nb 0.07 Zr 0.07 V 0.07 Co 0.07 Fe 0.07 Ni 0.07 Ru 0.3 The polarization curves of the O2 electrode and the commercial ruthenium-iridium DSA electrode in neutral electrolyte for the electrocatalytic production of hypochlorous acid show that Zr 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru 0.3 O2, Sn 0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 O2, Ti 0.2 Sn 0.2 Sb 0.3 Ru 0.3 O2, Nb 0.2 Zr 0.2 V 0.3 Ru 0.3 O2, Co 0.1 Fe 0.1 Ni 0.1 Ru 0.7 O2, Ti 0.14 Sn 0.07 Sb 0.07 Nb 0.07 Zr 0.07 V 0.07 Co 0.07 Fe 0.07 Ni 0.0 7Ru 0.3 The O2 electrode exhibits superior peak potential and current growth rate compared to commercial ruthenium-iridium DSA electrodes.

[0324] Application Example 8

[0325] Electrochemical performance test of a low-noble-metal mixed oxide electrode used for electrocatalytic chloride ion oxidation in alkaline brine.

[0326] The electrodes obtained in Examples 1, 3, 5, 7, 9, 10, 11, and 12, and a commercial ruthenium-iridium DSA electrode were tested for their electrocatalytic production of hypochlorite under alkaline conditions.

[0327] The test method is the same as in Application Example 1, except that the electrolyte is 1 mol L. -1 A potassium chloride solution (adjusted to pH=10 with potassium hydroxide) was used as the electrolyte.

[0328] Figure 15 A, B, C, D, E, F, G, H, and I represent Zr... 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru 0.3 O2, Sn 0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 O2, Ti 0.2 Sn 0.2 Sb 0.3 Ru 0.3 O2, Nb 0.2 Zr 0.2 V 0.3 Ru 0.3 O2, Co 0.1 Fe 0.1 Ni 0.1 Ru 0.7 O2, Ti 0.14 Sn 0.07 Sb 0.07 Nb 0.07 Zr 0.07 V 0.07 Co 0.07 Fe 0.07 Ni 0.07 Ru 0.3 The polarization curves of the O2 electrode and the commercial ruthenium-iridium DSA electrode in alkaline electrolyte for the electrocatalytic production of hypochlorite can be seen. 0.6 Sb 0.1 Ru 0.3 O2, Zr 0.6 V 0.1 Ru 0.3 O2, Sn0.6 Nb 0.1 Ru 0.3 O2, Sn 0.6 Ti 0.1 Ru 0.3 O2, Ti 0.2 Sn 0.2 Sb 0.3 Ru 0.3 O2, Nb 0.2 Zr 0.2 V 0.3 Ru 0.3 O2, Co 0.1 Fe 0.1 Ni 0.1 Ru 0.7 O2, Ti 0.14 Sn 0.07 Sb 0.07 Nb 0.07 Zr 0.07 V 0.07 Co 0.07 Fe 0.07 Ni 0.0 7Ru 0.3 The O2 electrode exhibits superior peak potential and current growth rate compared to commercial ruthenium-iridium DSA electrodes.

[0329] As can be seen from Application Examples 1, 7 and 8, the low-noble metal mixed oxide electrode obtained by the sol-gel method exhibits better electrochemical performance than the commercial ruthenium-iridium DSA electrode in chloride-containing solutions under different pH conditions (0-10).

Claims

1. An energy cycle system based on hydrochloric acid electrolysis, characterized in that, The energy cycle system includes: a hydrochloric acid storage device (1), an electrolytic hydrochloric acid hydrogen and chlorine evolution system (2), a hydrogen storage device (5), a chlorine storage device (6), and a hydrogen-chlorine fuel cell (7); The hydrochloric acid storage device (1) is connected to the anode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system (2) via a hydrochloric acid input pipe (101), or the hydrochloric acid storage device (1) is connected to the anode and cathode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system (2) via a hydrochloric acid input pipe (101). The anode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system (2) is connected to the chlorine storage device (6), and the chlorine storage device (6) is connected to the cathode of the hydrogen-chlorine fuel cell (7) via a chlorine input pipe (109). The cathode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system (2) is connected to the hydrogen storage device (5), and the hydrogen storage device (5) is connected to the anode of the hydrogen-chlorine fuel cell (7) through the hydrogen input pipe (108). The cathode of the hydrogen-chlorine fuel cell (7) is also connected to the hydrochloric acid storage device (1).

2. The energy cycle system based on hydrochloric acid electrolysis according to claim 1, characterized in that, The energy cycle system also includes a chlorine separation device (4); The anode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system (2) is connected to the chlorine separation device (4) through the chlorine / hydrochloric acid output pipe (102), and the chlorine separation device (4) is connected to the chlorine storage device (6) through the chlorine output pipe (105). The chlorine storage device (6) is equipped with a chlorine compression device, or a chlorine compression device is provided between the chlorine output pipe (105) and the chlorine storage device (6).

3. The energy cycle system based on hydrochloric acid electrolysis according to claim 2, characterized in that, The lower part of the chlorine separation device (4) is connected to the hydrochloric acid storage device (1) through the second hydrochloric acid reflux pipe (107).

4. The energy cycle system based on hydrochloric acid electrolysis according to claim 1, characterized in that, The energy cycle system also includes a hydrogen separation device (3); The cathode of the electrolytic hydrochloric acid hydrogen and chlorine evolution system (2) is connected to the hydrogen separation device (3) through the hydrogen / hydrochloric acid output pipe (103), and the hydrogen separation device (3) is connected to the hydrogen storage device (5) through the hydrogen output pipe (104). The lower part of the hydrogen separation device (3) is connected to the hydrochloric acid storage device (1) through the first hydrochloric acid reflux pipe (106).

5. The energy cycle system based on hydrochloric acid electrolysis according to claim 1, characterized in that, The energy cycle system also includes a chlorine / hydrogen chloride separation unit (8); The cathode of the hydrogen-chlorine fuel cell (7) is connected to the chlorine / hydrogen chloride separator (8) via a chlorine / hydrogen chloride output pipe (111). The upper part of the chlorine / hydrogen chloride separator (8) is connected to the chlorine storage device (6) via a chlorine return pipe (112). The lower part of the chlorine / hydrogen chloride separator (8) is connected to the hydrochloric acid storage device (1).

6. The energy cycle system based on hydrochloric acid electrolysis according to claim 5, characterized in that, The energy recycling system also includes a hydrochloric acid recovery and purification device (9); The lower part of the chlorine / hydrogen chloride separation device (8) is connected to the hydrochloric acid recovery and purification device (9) through a hydrochloric acid / saturated brine transport pipeline (113). One outlet of the hydrochloric acid recovery and purification device (9) is connected to the hydrochloric acid storage device (1) through a hydrogen chloride reflux pipeline (115). The other outlet of the hydrochloric acid recovery and purification device (9) is connected to the chlorine / hydrogen chloride separation device (8) through a saturated brine reflux pipeline (114).

7. The energy cycle system based on hydrochloric acid electrolysis according to claim 1, characterized in that, The anode of the hydrogen-chlorine fuel cell (7) is also connected to the hydrogen storage device (5) via a hydrogen return pipe (110).

8. The energy cycle system based on hydrochloric acid electrolysis according to claim 1, characterized in that, The anode in the electrolytic hydrochloric acid hydrogen and chlorine evolution system (2) is a mixed metal oxide electrode. The hybrid metal oxide electrode comprises a conductive substrate and a hybrid metal oxide loaded on the conductive substrate, wherein the molecular formula of the hybrid metal oxide is M. x Ru 1-x O2; Where M represents two or more of Ti, Sn, Sb, Nb, Zr, V, Co, Fe, and Ni; x is the mole fraction of all metals in M ​​and M x Ru 1-x The ratio of the mole fractions of all metals in O2, x = 20-70%.

9. A method for operating the energy cycle system based on hydrochloric acid electrolysis as described in any one of claims 1 to 8, characterized in that, The working method includes: Electrical energy is connected to the electrolytic hydrochloric acid hydrogen and chlorine evolution system (2). The hydrochloric acid provided in the hydrochloric acid storage device (1) is used as the electrolyte. Chlorine evolution reaction and hydrogen evolution reaction occur to obtain chlorine and hydrogen. The chlorine output in this process is sent to the chlorine storage device (6) for storage and waiting for use. The hydrogen output in this process is sent to the hydrogen storage device (5) for storage and waiting for use. The gases in the chlorine storage device (6) and the hydrogen storage device (5) are respectively input to the cathode and anode of the hydrogen-chlorine fuel cell (7). In the hydrogen-chlorine fuel cell (7), chlorine and hydrogen react to produce hydrogen chloride and generate electricity. The hydrogen chloride flows back to the hydrochloric acid storage device (1) for recycling.

10. The operating method of the energy cycle system based on hydrochloric acid electrolysis according to claim 9, characterized in that, Chlorine is pressurized and liquefied in the chlorine storage device (6), or is pressurized and liquefied before being sent to the chlorine storage device (6).

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