Electrolysis method for chloride ion-containing water, electrolysis apparatus, and layered electrode

Abstract

The present invention relates to an electrolysis method for chloride ion-containing water, an electrolysis apparatus, and a layered electrode. The electrolysis method for chloride ion-containing water of the present invention comprises the following steps: bringing chloride ion-containing water into contact with a chloride ion selective barrier material to obtain treated water; and then bringing the treated water into contact with an electrode to cause a decomposition reaction of water to obtain oxygen and hydrogen, and simultaneously obtain undecomposed water, wherein the chloride ion selective barrier material is selected to satisfy at least one condition explicitly defined in the description. In the present invention, by using the selective chloride ion selective barrier material, the reaction efficiency is improved while chloride ion adsorption is suppressed, and the operation method is simple and more readily facilitates large-scale production, thereby providing the present invention with significant production advantages.

Description

An electrolysis method, electrolysis apparatus and layered electrode for chloride-containing water Technical Field

[0001] This invention relates to the field of hydrogen production by electrolysis. More specifically, this invention relates to a method, apparatus, and layered electrode for electrolyzing chloride-containing water. Background Technology

[0002] Electrolysis of water is an ideal route for producing green hydrogen. Currently, hydrogen production through electrolysis mainly relies on pure water methods such as alkaline water production, PEM (pure water-based hydrogen production), AEM (alkaline water-based hydrogen production), and SOEC (sodium carbonate-based hydrogen production). However, freshwater resources are scarce, and even freshwater needs to be purified before it can be used as a raw material, increasing the cost of hydrogen production. Globally, seawater and industrial saline wastewater resources are abundant, providing an endless source of raw materials for electrolysis of water. However, these low-quality water sources contain large amounts of chloride ions, which not only corrode the electrodes but also cause chlorine evolution at the anode, competing with oxygen evolution and affecting the efficiency of the electrolyzer.

[0003] Chinese patent application CN113445061A discloses a flat-tube solid oxide electrolyzer, a seawater electrolysis hydrogen production device, and a process for hydrogen production. It employs a uniquely structured solid oxide electrolyzer to directly electrolyze untreated natural seawater at high temperatures. The seawater is heated and evaporated, and hydrogen is used as a carrier gas to carry varying amounts of water vapor for electrolysis at 750°C. However, this technology is immature, difficult to implement, and costly.

[0004] Chinese patent application CN114016052A discloses a continuous seawater electrolysis hydrogen production system and its operating method. This system includes an electrolysis module and a sodium chloride deposition module, separating the sodium chloride deposition process from the electrolysis system. This allows for the separation of sodium chloride from the electrolysis system without affecting electrolysis, thus achieving continuous operation of the seawater electrolysis hydrogen production system. However, this system does not consider the problem of ineffective chloride ion migration, resulting in slightly lower electrolysis efficiency. Currently disclosed technical methods focus more on chloride ion corrosion and do not consider the increased energy consumption caused by ineffective current due to a large amount of chloride ion migration. Summary of the Invention

[0005] The inventors of this invention have discovered that conventional electrolyzer gradation methods suffer from problems such as competitive precipitation, low electrolysis efficiency, and ineffective ion migration in the electrolysis of chloride-containing water to produce hydrogen. Based on this discovery, this invention provides an electrolysis method and apparatus for chloride-containing water. By adding a chloride-selective barrier material to the conventional "cathode-membrane-anode" gradation method, this material can inhibit chloride ion adsorption at the anode, thereby avoiding competitive precipitation at the anode, and can also block ineffective chloride ion migration across the membrane, thus improving electrolysis efficiency.

[0006] According to a first aspect of the present invention, a method for electrolyzing chloride-containing water is provided, comprising the following steps:

[0007] Chloride-containing water is contacted with a chloride-selective barrier material to obtain treated water. This treated water is then contacted with electrodes to induce a water decomposition reaction, producing oxygen and hydrogen, while simultaneously yielding undecomposed water.

[0008] The chloride ion selective blocking material is selected to satisfy at least one of the following conditions:

[0009] 1) The chloride ions (Cl) in the chloride-containing water 1- The content of ) (denoted as CO, in wt%) and the chloride ions (Cl) in the undecomposed water 1- The ratio of the content of (C1, in wt%) of C0 / C1 is 1.0-1.5 (preferably 1.1-1.4).

[0010] 2) The chloride ions (Cl) in the chloride-containing water 1- The content of chloride ions is 0-7.0 wt% (preferably 0-3.0 wt%). Based on a total weight of 100 wt% for the chloride-containing water, the chloride ion content (Cl...) of the chloride-containing water is... 1- When the content of ) is 0wt%, at 2000A / m 2 Let Y be the current efficiency of hydrogen production during the decomposition reaction, and let Y be the chloride ion concentration (Cl) of the chloride-containing water. 1- When the content of ) is 7.0 wt%, the current efficiency of hydrogen production when the decomposition reaction occurs at the same current density is Y', then Y' / Y is 0.99-1.0 (preferably 0.995-1.0).

[0011] According to a second aspect of the invention, there is a layered electrode comprising an electrode and a chloride ion selective blocking material layer, wherein Q0 / Q1 is 0.98-1.0 (preferably 0.99-1.0) and I0 / I1 is 0.98-1.0 (preferably 0.99-1.0).

[0012] According to a third aspect of the invention, there is an electrolysis apparatus for chloride-containing water, comprising an electrolysis cell for containing the chloride-containing water and a layered electrode of the invention.

[0013] According to a fourth aspect of the present invention, a method for manufacturing a layered electrode is provided, comprising the following steps:

[0014] A cathode slurry containing a cathode catalyst is coated onto one side of an anion exchange membrane, followed by a first hot-pressing treatment to form a cathode on one side of the anion exchange membrane.

[0015] An anode slurry containing an anode catalyst is coated onto the other side of the anion exchange membrane, followed by a second hot-pressing treatment to form an anode on the other side of the anion exchange membrane.

[0016] A slurry containing a chloride ion selective blocking material is applied to at least one location: the outer side of the cathode, between the cathode and the anion exchange membrane, and between the anode and the anion exchange membrane. Then, a third hot-pressing treatment is performed.

[0017] According to a fifth aspect of the present invention, a method for manufacturing a layered electrode is provided, comprising the following steps:

[0018] A pre-formed cathode is positioned on one side of the anion exchange membrane by pressure, a pre-formed anode is positioned on the other side of the anion exchange membrane by pressure, and a pre-formed chloride ion selective barrier material layer is positioned at least at one location: outside the cathode, between the cathode and the anion exchange membrane, and between the anode and the anion exchange membrane by pressure.

[0019] Technical effect

[0020] The technical solution of the present invention has the following advantages:

[0021] (1) The electrolysis method described in this invention adds a chloride ion selective barrier material to the conventional "cathode, exchange membrane, anode" structure. The addition of this material can suppress the adsorption of chloride ions on the electrode surface, while allowing the target hydroxide ions to pass through, thereby achieving efficient and directional selective adsorption of hydroxide ions, solving the problem of avoiding competitive precipitation of chloride ions at the anode, and thus improving the electrolysis efficiency.

[0022] (2) By setting a chloride ion selective barrier material, the present invention can effectively reduce the ineffective migration of chloride ions on both sides of the anode and cathode, improve the current efficiency of the hydrogen production process, and thus reduce the energy consumption generated in the electrolytic hydrogen production process; in addition, the ineffective migration of its cations can be suppressed by the preferred exchange membrane, further reducing the energy consumption of hydrogen production.

[0023] (3) This invention improves reaction efficiency by using a selective chloride ion selective barrier material to inhibit chloride ion adsorption. The operation method is simple and easy to realize large-scale production, giving it significant production advantages. Attached Figure Description

[0024] Figure 1 is a schematic diagram of the electrolysis device of the present invention.

[0025] Figure 2 shows the results of the electrolyte after reaction in Example 1 of the present invention measured by ultraviolet-visible spectrophotometry. Detailed Implementation

[0026] The specific embodiments of the present invention will be described in detail below. However, it should be noted that the scope of protection of the present invention is not limited to these specific embodiments, but is determined by the claims in the appendix.

[0027] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0028] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0029] In the context of this invention, all numerical values ​​of parameters (e.g., quantity or condition) should be understood to be modified by the term “about” in all cases, regardless of whether “about” actually appears before the numerical value.

[0030] In the context of this invention, "substantially" means that deviations that are acceptable or reasonable to those skilled in the art are permitted, such as deviations within ±2%, ±1%, ±0.5%, or ±0.1%.

[0031] In the context of this invention, the average transverse and average longitudinal dimensions of the anion intercalation material are measured using a scanning electron microscope. The specific testing steps are as follows: after fixing the sample to the test plate with conductive adhesive, it is transferred into the test chamber and vacuumed. After the system conditions are met, the sample morphology is observed. The test scale range is 1-5000nm. The interlayer spacing d(003) is measured as follows: the θ value corresponding to d(00) is obtained through the XRD results of the sample, which is generally in the range of 5-15°. The obtained θ value is calculated using the Bragg formula 2d(003)sinθ=nλ to obtain the corresponding interlayer spacing d(003), where θ is the peak position, n is the diffraction order, and λ is the wavelength of the X-ray.

[0032] In the context of this invention, the specific surface area, pore volume, pore size, or average pore size of the anion intercalation material is measured using a nitrogen adsorption / desorption test, wherein the test medium is nitrogen, the test temperature is -196°C, the specific surface area is calculated using the BET method, and the pore size and pore volume are calculated using the BJH method.

[0033] In the context of this invention, the method for measuring the metal element content in anion intercalation materials is ICP-MS (inductively coupled plasma atomic emission spectrometry). The sample is digested and prepared into a solution with a concentration range of 0-100 ppm for testing, and then the test results are converted into the actual concentration.

[0034] In the context of this invention, the anion content in the anion intercalation material can be determined using ion chromatography and organic elemental analysis. Ion chromatography can determine nitrate, chloride, sulfate, and phosphate ions. Specifically, the solid is dissolved in acid to prepare a solution with a concentration of 0-50 ppm, which is then introduced into a chromatographic column for testing. Organic elemental analysis can determine the concentration of carbonate ions. The precursor sample is heated to 900°C in a pure oxygen environment, and the generated gas is separated by a chromatographic column and the carbon content is obtained by passing it through a TCD detector. The carbonate ion content is then deduced from this carbon content.

[0035] In the context of this invention, the method for measuring the chloride ion content in water is ion chromatography, and the method is as follows: the chloride ion concentration is diluted to 0-50 ppm and injected into a chromatographic column for testing.

[0036] In the context of this invention, the current density is measured as follows: the anode, membrane, cathode, and chloride ion selective barrier material are assembled into the electrolytic cell in the order described above, 25 wt% alkaline seawater is introduced, the small chamber voltage is kept constant, the real-time current is tested, and the current density is obtained by dividing the current by the working area.

[0037] In the context of this invention, the current efficiency is measured by the ratio of the real-time hydrogen production to the hydrogen production calculated by the current method. The current method calculation formula is Q = Inη / 2390, where Q is the theoretical hydrogen production, n is the number of chambers, and η is the electrolysis efficiency (calculated at 100%). The real-time hydrogen production can be observed by the pipeline flow meter.

[0038] In the context of this invention, the ultraviolet-visible spectrophotometric measurement method employs a full-wavelength scanning method with a scanning range of 200-800 nm and a sampling interval of 4 h.

[0039] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this instruction manual are based on weight, and the pressure is gauge pressure.

[0040] In the context of this invention, any two or more embodiments or aspects of this invention can be arbitrarily combined, and the resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of this invention.

[0041] According to one embodiment of the present invention, a method for electrolyzing chloride-containing water, particularly a method for electrolyzing seawater, is provided. Except as specifically described below, all matters or practices conventionally known in the art related to water electrolysis are directly applicable to this invention and will not be repeated here.

[0042] According to one embodiment of the present invention, the electrolysis method includes the steps of: contacting chloride-containing water with a chloride-selective barrier material to obtain treated water, and then contacting the treated water with an electrode to undergo a water decomposition reaction to obtain oxygen and hydrogen, while simultaneously obtaining undecomposed water. According to the present invention, the chloride-containing water is first contacted with the chloride-selective barrier material and then with the electrode; this is the key to the present invention's ability to achieve the desired technical effect. Specifically, after chloride-containing water enters the electrolyzer, it first passes through a chloride ion selective barrier material, then sequentially through electrodes and membranes. The chloride ion selective barrier material is a core-shell structure of anion-modified layered electrodes wrapped with carbon layers. The carbon layer structure protects the internal catalytic layer, thus improving the stability of the chloride ion selective barrier material, and also adsorbs hydroxide and chloride ions. Simultaneously, the unique structure of the carbon layer improves the overall conductivity of the chloride ion selective barrier material, thereby reducing the reaction overpotential. The core is anion-modified composite structure with good oxygen evolution catalytic activity. Furthermore, the anion modification gives the core a certain degree of repulsion against chloride ions, preventing their accumulation and ineffective migration on the electrode surface, thus achieving selective adsorption of hydroxide ions. In addition, the chloride ion selective barrier material itself possesses electrocatalytic activity, therefore it also improves the hydrogen production efficiency.

[0043] According to one embodiment of the present invention, by selecting the chloride ion selective blocking material, condition 1) is satisfied: the chloride ions (Cl...) in the chloride-containing water... 1- The content of ) (denoted as CO, in wt%) and the chloride ions (Cl) in the undecomposed water 1- The ratio of the content of chloride ions (C1, in wt%) to C0 / C1 is 1.0-1.5 (preferably 1.1-1.4). Furthermore, according to the present invention, by selecting the chloride ion selective blocking material, condition 2) is satisfied: the chloride ion content (Cl...) of the chloride-containing water... 1- The content of chloride ions in the chloride-containing water is 0-7 wt% (preferably 0-3 wt%). Assuming the total weight of the chloride-containing water is 100 wt%, the chloride ion content (Cl...) in the chloride-containing water is... 1- When the content of ) is 0wt%, at 2000A / m 2 Let Y be the current efficiency of hydrogen production during the decomposition reaction, and let Y be the chloride ion concentration (Cl) of the chloride-containing water. 1-When the content of ) is 7wt%, the current efficiency of hydrogen production during the decomposition reaction at the same current density is Y', then Y' / Y is 0.99-1.0 (preferably 0.995-1.0). The inventors of this invention have discovered that, when conditions 1 and 2 are met, the electrolysis method and electrolysis device provided by this invention can effectively suppress the side reaction of chloride ions at the anode, while simultaneously improving the adsorption capacity of target hydroxide ions, thereby improving the selectivity of the oxygen evolution reaction, and minimizing the ineffective migration of chloride ions across the membrane, thereby improving the current efficiency and hydrogen production efficiency. If conditions 1 or 2 are not met, there may be a risk of crystal precipitation due to excessively high electrolyte solute content, increasing the probability of side reactions and decreasing electrolysis efficiency. Without any theoretical limitations, the inventors of this invention believe that the electrolysis method and electrolysis device provided by this invention can use different membrane materials and electrode materials, and can be applied to full pH electrolysis hydrogen production conditions, including chlorine-free or chlorine-containing conditions, and other low-quality water source hydrogen production conditions containing anionic or cationic impurities, depending on the specific scenario. Furthermore, this invention possesses selective ion purification capabilities under certain operating conditions, and therefore can be applied to the desalination and purification of low-quality water sources.

[0044] According to a preferred embodiment of the present invention, by selecting the chloride ion selective blocking material, condition 1) is satisfied: assuming the time at which the decomposition reaction begins is t0 (in hours), then after t0+200 (i.e., 200 hours after the start), CO' / Cl' is 0.15-0.9 (preferably 0.2-0.6). Furthermore, according to the present invention, by selecting the chloride ion selective blocking material, condition 2) is satisfied: the chloride ions (Cl...) in the chloride-containing water... 1- The content of chloride ions is 0.2-7 wt% (preferably 0.2-5 wt%). Based on a total weight of 100 wt% for the chloride-containing water, the chloride ion content (Cl...) of the chloride-containing water is... 1- When the content of ) is 0.2wt%, at 2000A / m 2 The current density at which the decomposition reaction occurs is given by the current efficiency of hydrogen production as Y1. Let the chloride ion concentration (Cl) in the chloride-containing water be... 1- When the content of chloride ions is 5 wt%, the current efficiency for producing hydrogen during the decomposition reaction at the same current density is Y1′, and Y1′ / Y1 is 0.992-1.0 (preferably 0.996-1.0). The inventors of this invention have discovered that when conditions 1 and 2 are simultaneously met, the high efficiency of the hydrogen production reaction during the electrolysis of water containing chloride ions can be guaranteed, while the interference of chloride ions can be suppressed. When condition 1 is met but condition 2 is not, there is an excessive amount of ineffective chloride ion migration, leading to a decrease in electrolysis efficiency; when condition 2 is met but condition 1 is not, there may be problems such as excessive or insufficient circulating liquid volume leading to increased energy consumption or untimely bubble removal.

[0045] According to a preferred embodiment of the present invention, the treated water is brought into contact with the cathode and the anode sequentially. The chloride-containing water is located outside the cathode (and also outside the chloride-selective blocking material), referred to as the cathode-outer electrolyte, and the undecomposed water is located outside the anode, referred to as the anode-outer electrolyte. Preferably, the treated water is brought into contact with the anode last. The inventors of this invention have discovered that when the chloride-containing water passes through the chloride-selective blocking material before entering the cathode, the directional selective adsorption of the chloride-selective blocking material ensures that chloride ions in the system accumulate on the cathode side. This not only prevents ineffective chloride ion migration but also fundamentally blocks the chloride evolution side reaction on the anode side.

[0046] According to one embodiment of the present invention, the chloride-containing water (referred to as first chloride-containing water) is provided from the side of the electrode adjacent to the chloride ion selective blocking material, and the chloride-containing water (referred to as second chloride-containing water) is provided from the opposite side of the electrode, wherein the second chloride-containing water mixes with the undecomposed water to form mixed water. In the context of this specification, unless otherwise specified, the mixed water and the undecomposed water are not distinguished and are collectively referred to as undecomposed water.

[0047] According to one embodiment of the present invention, based on a total weight of 100 wt% of the chloride-containing water, chloride ions (Cl... 1- The chloride ion content is 0-7 wt% (preferably 0-3 wt%), with the balance being water and unavoidable impurities. Here, the unavoidable impurities are those conventionally known to those skilled in the art, such as sulfate ions (0.23-5 wt%), alkali metal ions such as sodium and potassium (1.2-10 wt%), nitrate ions (0.0011-0.5 wt%), bromine and iodine (0.02-0.5 wt%), and alkaline earth metal ions such as calcium and magnesium (0.18-1 wt%). Seawater is preferred as the chloride-containing water.

[0048] According to one embodiment of the present invention, without mixing with the second chloride-containing water, based on 100 wt% of the total weight of the undecomposed water, chloride ions (Cl... 1- The content of the component is 0-7 wt% (preferably 0-5 wt%), with the balance being water and unavoidable impurities. Here, the unavoidable impurities are those conventionally known to those skilled in the art, such as sulfate ions (0.23-5 wt%), alkali metal ions such as sodium and potassium (1.2-10 wt%), nitrate ions (0.0011-0.5 wt%), bromine and iodine (0.02-0.5 wt%), and alkaline earth metal ions such as calcium and magnesium (0.18-1 wt%).

[0049] According to one embodiment of the present invention, the chloride ion selective blocking material is a porous material. Since the ineffective migration of chloride ions can induce ineffective current, leading to a decrease in current efficiency, the chloride ion blocking rate of the chloride ion selective blocking material can be determined by the current efficiency through its ratio to the hydroxide ion permeability. Specifically, the hydrogen production and current value are tested under 20wt% alkaline solution and 20wt% alkaline seawater conditions at a fixed current density. Let Q0 be the measured hydrogen production under 20wt% alkaline seawater conditions, Q1 be the measured hydrogen production under alkaline solution conditions, I0 be the current value under 20wt% alkaline seawater conditions, and I1 be the measured current value under alkaline solution conditions. The ratios Q0 / Q1 and I0 / I1 are 0.98-1.0 (preferably 0.99-1.0).

[0050] According to one embodiment of the present invention, the operating conditions of the decomposition reaction include: operating temperature: 20-90℃, operating pressure: 0-2.5MPaG, and operating voltage: 1.7-2.2V.

[0051] According to one embodiment of the present invention, the electrode sequentially comprises a cathode, an anion exchange membrane, and an anode, wherein the chloride ion selective blocking material is disposed in layers at least at one location: outside the cathode, between the cathode and the anion exchange membrane, and between the anode and the anion exchange membrane. Preferably, the chloride ion selective blocking material is disposed in layers outside the cathode. In this case, the cathode, the anion exchange membrane, and the anode are all in contact only with the treated water, thereby avoiding adverse effects from the chloride-containing water.

[0052] According to one embodiment of the present invention, the cathode, the anion exchange membrane, the anode, and the chloride ion selective blocking material layer are independently layered and stacked together in a zero-gap manner to form a whole. Here, "zero-gap" means that the chloride ion selective blocking material, cathode, exchange membrane, and anode are arranged as closely as possible in sequence. The inventors of the present invention have found that the zero-gap method can effectively shorten the ion transport path and maximize the contact area, thus resulting in higher electrolysis efficiency. Simultaneously, the zero-gap method can effectively reduce the spacing between the chambers of the electrolytic cell, achieving the goal of reducing the overall volume and weight of the electrolytic cell. If the zero-gap method is not used, the chloride ion blocking effect will not be affected, but the electrolysis efficiency will decrease, and the overall volume of the electrolytic cell may increase.

[0053] According to one embodiment of the invention, a layered electrode is also provided. According to the invention, the layered electrode is particularly suitable for use as an electrode in the electrolysis method for chloride-containing water of the invention.

[0054] According to one embodiment of the present invention, the layered electrode comprises multiple layers, particularly including an electrode (forming a layer) and a chloride ion selective blocking material layer. According to the present invention, the chloride ion selective blocking material is a porous material. Since ineffective migration of chloride ions can induce ineffective current, leading to a decrease in current efficiency, the chloride ion blocking rate of the chloride ion selective blocking material layer can be determined by the current efficiency through its interaction with the hydroxide ion permeability. Specifically, the hydrogen production and current value are tested under 20wt% alkaline solution and 20wt% alkaline seawater conditions at a fixed current density. Let Q0 be the measured hydrogen production under 20wt% alkaline seawater conditions, Q1 be the measured hydrogen production under alkaline solution conditions, I0 be the current value under 20wt% alkaline seawater conditions, I1 be the measured current value under alkaline solution conditions, Q0 / Q1 be 0.98-1.0 (preferably 0.99-1.0), and I0 / I1 be 0.98-1.0 (preferably 0.99-1.0).

[0055] According to one embodiment of the present invention, the electrode sequentially includes a cathode, an anion exchange membrane, and an anode, and the chloride ion selective blocking material layer is disposed at at least one location: outside the cathode, between the cathode and the anion exchange membrane, and between the anode and the anion exchange membrane. Preferably, the chloride ion selective blocking material layer is disposed outside the cathode.

[0056] According to one embodiment of the present invention, the thickness of the cathode is 1-800 micrometers, the thickness of the anion exchange membrane is 80-1000 micrometers, the thickness of the anode is 1-800 micrometers, and the thickness of the chloride ion selective blocking material layer is 1-800 micrometers (preferably 20-500 micrometers).

[0057] According to the present invention, the specific selection of the anode catalyst in the anode is not limited, and it can be a conventional anode catalyst in the field of layered electrodes, such as a metal element, alloy, metal or non-metal compound with corresponding activity. According to one embodiment of the present invention, the anode catalyst contains at least one of nickel (Ni), iron (Fe), cobalt (Co), manganese (Mn), molybdenum (Mo), aluminum (Al), and alloys of any two or more of these components. By selecting the above-mentioned highly active and selective anode catalyst, the oxygen evolution reaction can still occur to the maximum extent at the anode even in the presence of some chloride ions, thereby improving hydrogen production efficiency. Specifically, the anode catalyst can be one or more of the elements, alloys, nitrides, phosphides, oxides, and hydroxides of Ni, Fe, Co, Mn, Mo, and Al. Generally, the loading of the anode catalyst in the anode is 1.0-10.0 mg / cm³. 2 (Preferred concentration: 4.5-9.0 mg / cm³) 2 ).

[0058] The present invention does not limit the specific selection of the cathode catalyst in the cathode, and it can be a conventional cathode catalyst in the field of water electrolysis for hydrogen production, such as a metal element, alloy, metal or non-metal compound with corresponding activity. According to one embodiment of the present invention, the cathode catalyst contains at least one of nickel, iron, cobalt, manganese, and alloys of any two or more of these components. Specifically, the cathode catalyst can be one or more of the elements, alloys, nitrides, phosphides, oxides, and hydroxides of Ni, Fe, Co, and Mn. Generally, the loading of the cathode catalyst in the cathode is 0.5-8.0 mg / cm³. 2 (Preferred concentration: 4.5-7.5 mg / cm³) 2 ).

[0059] According to the present invention, the specific selection of the anion exchange membrane is not limited. In some embodiments, the functional groups of the anion exchange membrane are selected from at least one of primary amines, secondary amines, tertiary amines, quaternary amines, and aromatic amines. The function of the functional groups is to modify the polymer backbone to achieve directional selection of anions. In some embodiments, based on the matrix backbone material, the anion exchange membrane can be a fluoropolymer membrane such as polytetrafluoroethylene or fluorinated poly(aryl ethers), or a non-fluorocarbon polymer membrane such as polysulfones, polyphenylene ethers, polyaryl ether ketones, polyvinylpyridines, and polynorbornene. By employing anion exchange membranes, anions can pass through directionally, while cations are restricted, resulting in better ionic conductivity. Combined with the function of the chloride ion selective blocking material layer, chloride ions cannot be transported through the membrane material, thereby further suppressing the competitive deposition of chloride ions at the anode.

[0060] According to one embodiment of the present invention, the chloride ion selective blocking material is selected from at least one of anion-intercalated materials, sulfides, phosphides, and nitrides, particularly anion-intercalated layered metal hydroxides, anion-intercalated layered bimetallic hydroxides (LDHs), or chloride ion-intercalated LDHs, preferably chloride ion-intercalated hydrotalcite materials, and particularly preferably chloride ion-intercalated nickel-iron-based hydrotalcites. As a dosage, the loading of chloride ion selective blocking material in the chloride ion selective blocking material layer is generally 0.5-8.0 mg / cm³. 2 (Preferred dosage: 3.0-6.0 mg / cm³) 2 ).

[0061] According to one embodiment of the present invention, the anionic intercalating material comprises at least two metallic elements selected from nickel, iron, cobalt, manganese, aluminum, copper, zinc, chromium, zirconium, and magnesium, preferably at least two metallic elements selected from nickel, iron, cobalt, and manganese. It should be noted that the metallic elements in the hydrotalcite refer to the metallic elements that form the hydrotalcite; the final hydrotalcite may also contain metallic elements provided by the chloride ion intercalating agent. Furthermore, the anions used as the anionic intercalating material can specifically be at least one selected from sulfate ions, carbonate ions, nitrate ions, phosphate ions, and chloride ions, preferably chloride ions. Generally, based on a total weight of 100 wt% of the anionic intercalating material, the total content of the metallic elements is 55-90 wt% (preferably 65-85 wt%), and the content of the anions is 2-5 wt% (preferably 3.5-4.8 wt%). Additionally, when at least two of the metallic elements are included, the molar ratio between the different metallic elements is 1:1-10:1 (preferably 1:1-6:1).

[0062] According to one embodiment of the present invention, the anion intercalation material has a layered structure with an average lateral dimension of 500-2000 nm (preferably 600-800 nm), an average longitudinal dimension of 1-100 nm (preferably 20-60 nm), and a specific surface area of ​​120-300 m². 2 / g, pore volume 0.35-0.55cm³ 3 / g, with an average pore size of 2-30nm and an interlayer spacing d(003) of 0.75-0.9nm.

[0063] According to one embodiment of the present invention, the cathode, the anion exchange membrane, the anode, and the chloride ion selective blocking material layer are each formed as independent layers, and are stacked together in a zero-spaced manner to form a whole. Here, "zero-spaced" means that the chloride ion selective blocking material, cathode, exchange membrane, and anode are arranged as closely as possible in sequence.

[0064] According to one embodiment of the present invention, an electrolysis apparatus for chloride-containing water, particularly a seawater electrolysis apparatus, is also provided, comprising an electrolysis cell for containing the chloride-containing water and the layered electrode of the present invention. According to the present invention, apart from the layered electrode, other aspects and considerations related to seawater electrolysis apparatus in the art are directly applicable to the present invention and will not be elaborated further here.

[0065] According to one embodiment of the present invention, a method for manufacturing a layered electrode is also provided, comprising the following steps: (1) coating a cathode slurry containing a cathode catalyst onto one side of an anion exchange membrane and performing a first hot-pressing treatment to form a cathode on one side of the anion exchange membrane; (2) coating an anode slurry containing an anode catalyst onto the other side of the anion exchange membrane and performing a second hot-pressing treatment to form an anode on the other side of the anion exchange membrane; (3) coating a chloride ion selective blocking material slurry containing a chloride ion selective blocking material onto at least one location, including the outer side of the cathode, between the cathode and the anion exchange membrane, and between the anode and the anion exchange membrane, and then performing a third hot-pressing treatment.

[0066] According to the present invention, the order of steps (1), (2), and (3) is not limited, as long as the adjacent catalyst layer is prepared before the chloride ion selective barrier material layer is prepared. For example, when the chloride ion selective barrier material layer is disposed on the outside of the cathode, the cathode can be prepared before the chloride ion selective barrier material layer is prepared.

[0067] According to one embodiment of the present invention, in step (1), the conditions for the first hot pressing treatment include: a temperature of 120-300°C, a pressure of 2-15 MPa, and a time of 1-30 min.

[0068] According to one embodiment of the present invention, in step (2), the conditions for the second hot pressing treatment include: a temperature of 120-300°C, a pressure of 2-15 MPa, and a time of 1-30 min.

[0069] According to one embodiment of the present invention, in step (3), the conditions of the third hot pressing treatment include: temperature of 120-300℃, pressure of 2-15MPa, and time of 1-30min.

[0070] According to the present invention, those skilled in the art will understand that when the chloride ion selective barrier material layer is located between the anode and the exchange membrane and / or between the cathode and the exchange membrane, if it is prepared by hot pressing, it can be carried out in accordance with the above method, the only difference being the different preparation order of each layer, which will not be elaborated here.

[0071] According to one embodiment of the present invention, the above-mentioned layered electrode is prepared by a transfer printing method. When the chloride ion selective blocking material layer is disposed on the outside of the anode and / or cathode, the preparation method of the layered electrode specifically includes:

[0072] a. An anode slurry containing an anode catalyst is coated onto a first transfer film, and a cathode slurry containing a cathode catalyst is coated onto a second transfer film. The first transfer film carrying the anode slurry and the second transfer film carrying the cathode slurry are placed on both sides of an anion exchange membrane, and an anode and a cathode are formed on both sides of the exchange membrane by a fourth hot-pressing treatment.

[0073] b. Apply a slurry containing a chloride ion selective blocking material onto a third transfer film, place the third transfer film containing the chloride ion selective blocking material slurry on the outside of the anode and / or cathode, and transfer it to the outside of the anode and / or cathode through a fifth hot pressing process.

[0074] According to one embodiment of the present invention, in step a, the conditions for the fourth hot pressing include: a temperature of 150-300°C, a pressure of 5-18 MPa, and a time of 1-10 min.

[0075] According to one embodiment of the present invention, in step b, the conditions for the fifth hot pressing include: a temperature of 150-300°C, a pressure of 10-18 MPa, and a time of 1-20 min.

[0076] According to one embodiment of the present invention, in step b, the first transfer film, the second transfer film, and the third transfer film can each be independently selected from any one of polytetrafluoroethylene film, polyimide film, polydimethylsiloxane film, silicone rubber sheet, and aluminum foil. For ease of operation, according to one embodiment of the present invention, the first transfer film, the second transfer film, and the third transfer film are selected in the same way.

[0077] According to one embodiment of the present invention, the cathode paste may further contain a first solvent and a first binder, the anode paste may further contain a second solvent and a second binder, and the chloride ion selective barrier material paste may further contain a third solvent and a third binder.

[0078] According to one embodiment of the present invention, the first adhesive, the second adhesive and the third adhesive are each independently selected from Nafion solution and / or PTFE solution.

[0079] According to one embodiment of the present invention, the first solvent, the second solvent, and the third solvent are each independently selected from at least one of deionized water, ethylene glycol, isopropanol, and glycerol.

[0080] According to one embodiment of the present invention, the mass ratio of the cathode catalyst, the first binder and the first solvent is 1:1.5-30:11-70, more preferably 1:4-20:11-50.

[0081] According to one embodiment of the present invention, the mass ratio of the anode catalyst, the second binder, and the second solvent is 1:1.5-30:10-70, more preferably 1:4-20:10-50.

[0082] According to one embodiment of the present invention, the mass ratio of the chloride ion selective barrier material, the third binder and the third solvent is 1:1.5-30:11-70, more preferably 1:4-20:11-50.

[0083] According to the present invention, it is understood that when the chloride ion selective barrier material layer is located between the anode and the anion exchange membrane and / or between the cathode and the anion exchange membrane, if the transfer method is used for preparation, the above method can be followed. The only difference is that the preparation order of each layer is different, which will not be elaborated here.

[0084] According to one embodiment of the present invention, the coating method can be spraying or coating, and there is no particular limitation.

[0085] According to one embodiment of the present invention, a method for manufacturing a layered electrode is also provided, comprising the following steps: disposing a pre-formed cathode on one side of an anion exchange membrane by means of pressure, disposing a pre-formed anode on the other side of the anion exchange membrane by means of pressure, and disposing a pre-formed chloride ion selective barrier material layer on at least one location, on the outside of the cathode, between the cathode and the anion exchange membrane, and between the anode and the anion exchange membrane, by means of pressure.

[0086] Specifically, a cathode slurry containing a cathode catalyst is coated onto one side of the anion exchange membrane, followed by a first hot-pressing treatment to form a cathode on that side. An anode slurry containing an anode catalyst is then coated onto the other side of the anion exchange membrane, followed by a second hot-pressing treatment to form an anode on that side. The coating order of the cathode and anode is not fixed, but the chloride ion selective blocking material slurry must be coated in the final step. Furthermore, the coating or spraying method is only one implementation method; the cathode, anode, and chloride ion selective blocking material can also be self-supporting materials grown in situ and then directly assembled in sequence.

[0087] Example

[0088] The present invention will be further described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0089] Example 1

[0090] (1) 4.38 g of nickel-molybdenum alloy cathode catalyst (nickel-molybdenum atomic ratio of 6:1) and 26 g of 5% Nafion solution were added to 104 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) and ultrasonically mixed to prepare a cathode slurry. This slurry was then coated onto one side of a 25*25 cm anion exchange membrane and subjected to hot pressing. The hot pressing conditions included a temperature of 120℃, a pressure of 5 MPa, and a time of 15 min to form a cathode on one side of the exchange membrane. The cathode catalyst loading in the cathode was 7 mg / cm³. 2 The cathode thickness is 80 micrometers.

[0091] (2) The anion exchange membrane is of model Versogen A80, and its functional group is a dimethylpiperidine ion functional group. The thickness of the exchange membrane is 80 micrometers.

[0092] (3) 3.1 g of chloride-intercalated nickel-iron-based hydrotalcite (as a chloride-selective barrier material with Q0 / Q1 of 0.998 and I0 / I1 of 0.998) and 37.5 g of 5% Nafion solution were added to 87.5 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) to prepare a chloride-selective barrier material slurry. This slurry was coated onto the cathode and hot-pressed at 200℃ and 15 MPa for 1 min to form a chloride-selective barrier material layer on the cathode surface. The chloride-selective barrier material loading in the chloride-selective barrier material layer was 5 mg / cm³. 2 The chloride ion selective barrier material layer has a thickness of 50 micrometers, a total nickel-iron content of 80 wt%, a chloride ion content of 4.0 wt%, and a nickel-iron molar ratio of 5:1. It has a layered structure with an average lateral dimension of 650 nm, an average longitudinal dimension of 22 nm, and a specific surface area of ​​140 m². 2 / g, pore volume 0.42cm 3 / g, with an average pore size of 5.2nm and an interlayer spacing d(003) of 0.8nm.

[0093] The method for manufacturing the chloride ion intercalated nickel-iron-based layered double hydroxide (LDH)@nitrogen-modified carbon core-shell catalyst is as follows: 694g of nickel nitrate, 173.6g of ferric nitrate, 1.73kg of urea, and 434g of sodium chloride are placed in a 70L reactor and stirred evenly. The mixture is reacted at 150℃ for 6h. After washing and drying, chloride ion-modified nickel-iron LDH is obtained. The LDH is then placed in 27.8g of resorcinol, 14L of formaldehyde, 10.4mL of ethylenediamine, and 2.78L of an aqueous ethanol solution (water to ethanol volume ratio of 7:3) and stirred at 25℃ for 24h. Finally, the LDH is calcined at 600℃ for 10h under an ammonia atmosphere to obtain the chloride ion intercalated LDH@nitrogen-modified carbon core-shell catalyst.

[0094] (4) An anode slurry was prepared by mixing 5.3 mg of cobalt-manganese-based anode catalyst (specifically cobalt-manganese phosphide, with a cobalt-manganese atomic ratio of 3:1 and a phosphorus content of 5.5 wt%), 83 g of 5% Nafion solution, and 59 g of isopropanol. The anode slurry was coated onto the other side of the exchange membrane a material and subjected to hot pressing. The hot pressing conditions included a temperature of 120°C, a pressure of 6 MPa, and a time of 20 min to form an anode with a thickness of 100 micrometers. The loading of the anode catalyst in the anode was 8.5 mg / cm³. 2 Finally, an electrolysis chamber is obtained, the structure of which is shown in Figure 1. From left to right, it includes an anode, an exchange membrane, a cathode, and a chloride ion selective barrier material layer.

[0095] (5) Using seawater as the water source, prepare a 20wt sodium hydroxide seawater solution as the electrolyte, whose chloride ion (Cl) 1- The content of [missing information] was 1.7 wt%, the current efficiency Y was 99.7%, Y' was 99.6%, and after 200 h of reaction, the Cl in the electrolyte was 43000 mg / L. At this time, C0 / C1 was 1.26, Y' / Y was 0.99, C0' / C1' was 0.50, and Y1' / Y1 was 0.998. Electrolysis was started under these conditions, with an operating temperature of 70℃, an operating pressure of 1.6 MPaG, and an operating chamber voltage of 2.0 V. The performance evaluation results are shown in Table 1.

[0096] Figure 2 shows the UV-Vis spectrophotometer test results of the electrolyte after the reaction, with a scanning wavelength of 200-800 nm. As can be seen from the figure, if sodium hypochlorite is present in the solution, a peak will appear at around 300 nm. If chloride ions in the electrolyte are deposited at the anode, the generated chlorine gas will produce hypochlorite ions, which will also appear at around 300 nm. However, in the results of Figure 2, the electrolyte after the reaction in Example 1 did not show any peak, indicating that no chloride evolution side reaction occurred at the anode. This shows that Example 1 can effectively suppress the chloride ion side reaction at the anode.

[0097] Example 2

[0098] (1) 4.4g of nickel-cobalt based anode catalyst (i.e., nickel-cobalt sulfide, where the nickel-cobalt ratio is 2:1 and the sulfur content is 3.2wt%) and 21g of 20% Nafion solution were added to 194g of ethylene glycol aqueous solution (obtained by mixing ethylene glycol and water in a volume ratio of 4:1) and ultrasonically mixed to prepare an anode slurry. 3.2g of nickel-aluminum alloy cathode catalyst (nickel-aluminum atomic ratio of 10:1) and 18.7g of 20% Nafion solution were added to 118g of ethylene glycol aqueous solution (obtained by mixing ethylene glycol and water in a volume ratio of 4:1) to prepare an anode slurry. A cathode slurry was prepared by ultrasonically mixing water at a volume ratio of 4:1. The anode slurry was then coated onto one polyimide film, and the cathode slurry was coated onto another polyimide film. The polyimide films carrying the cathode slurry and the anode slurry were placed on opposite sides of an exchange membrane, respectively. The membrane was then hot-pressed at 150°C and 18 MPa for 10 minutes to form an anode catalyst layer and a cathode catalyst layer on opposite sides of the membrane. The anode catalyst loading in the anode catalyst layer was 7 mg / cm³. 2 The loading of the cathode catalyst in the cathode catalyst layer is 5 mg / cm³. 2 The anode thickness is 88 micrometers and the cathode thickness is 65 micrometers.

[0099] (2) An anion exchange membrane that allows water and anions to pass through, model number EVE Energy W-75, the thickness of the exchange membrane is 75 micrometers.

[0100] (3) A chloride ion selective barrier material slurry was prepared by uniformly mixing 2.5 g of chloride ion intercalated modified cobalt-iron-based hydrotalcite@nitrogen-modified carbon layer (as a chloride ion selective barrier material, Q0 / Q1 is 0.998, I0 / I1 is 0.998), 162 mg of 20% Nafion solution, and 430 mg of ethylene glycol aqueous solution (obtained by mixing ethylene glycol and water at a volume ratio of 4:1) and coating it onto the side of the film carrying the cathode catalyst layer. The mixture was then hot-pressed at 300℃ and 10 MPa for 20 min to form a chloride ion selective barrier material layer on the cathode surface. The chloride ion selective barrier material loading in the layer was 4 mg / cm³. 2 The chloride ion selective barrier material layer has a thickness of 45 micrometers, a total cobalt-iron content of 82 wt%, a chloride ion content of 3.8 wt%, and a nickel-iron molar ratio of 4:1. It has a layered structure with an average lateral dimension of 700 nm, an average longitudinal dimension of 25 nm, and a specific surface area of ​​135 m². 2 / g, pore volume is 0.41cm 3 / g, with an average pore size of 5.3nm and an interlayer spacing d(003) of 0.82nm.

[0101] The method for manufacturing the chloride ion intercalated cobalt-iron-based hydrotalcite@nitrogen-modified carbon core-shell catalyst is as follows: 555g cobalt chloride, 278g ferric chloride, 139g potassium chloride and 2.1kg sodium hydroxide are placed in a 70L reactor and stirred evenly, and reacted at 110℃ for 20h. After washing and drying, chloride ion modified iron-cobalt hydrotalcite is obtained. It is then placed in a 35mg / mL glucose aqueous solution and stirred at 80℃ for 10h, and calcined at 800℃ for 10h under a nitrogen atmosphere to obtain a chloride ion selective blocking material, which has an N-doped carbon layer as the shell and a chloride-modified iron-cobalt-based hydrotalcite as the core.

[0102] (4) The materials obtained above are assembled into an electrolytic cell, and seawater is used as the water source. A 24wt% sodium hydroxide seawater solution is prepared as the electrolyte, whose chloride ion (Cl) content is... 1- The content of the active ingredient was 1 wt%, the current efficiency Y was 99.7%, Y' was 99.6%, and after 200 h of reaction, the concentration of Cl in the electrolyte was 25300 mg / L. At this point, the ratio of Cl to Co was 1.3, Y' to Y was 0.998, Co' to C1' was 0.49, and Y1' to Y1 was 0.997. Electrolysis was started under these conditions, with an operating temperature of 70℃, an operating pressure of 1.6 MPaG, and an operating chamber voltage of 2.0 V. The performance evaluation results are shown in Table 1.

[0103] Example 3

[0104] (1) 3.8g of nickel-iron based anode catalyst (nickel-iron nitride, nickel-iron atomic ratio of 5:1, nitrogen content of 3wt%) and 60g of 5% Nafion solution were added to 62.5g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 4:1) and ultrasonically mixed to prepare an anode slurry. 4.1g of nickel alloy based cathode catalyst (nickel sulfide, nickel content of 82wt%, sulfur content of 5wt%) and 40.6g of 5% Nafion solution were added to 180g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 1:1) and ultrasonically mixed to prepare a cathode slurry. Both slurries were coated onto both sides of a 25*25cm exchange membrane and subjected to hot pressing at 150℃, 15MPa, and for 10min. The loading of the anode catalyst in the anode catalyst layer was 6mg / cm². 2 The anode thickness is 76 micrometers, and the cathode catalyst loading in the cathode catalyst layer is 6.5 mg / cm³. 2 The cathode thickness is 78 micrometers.

[0105] (2) The anion exchange membrane is of model Versogen A80, and its functional group is a dimethylpiperidine ion functional group. The thickness of the exchange membrane is 80 micrometers.

[0106] (3) A directional selective catalytic slurry was prepared by uniformly mixing 3.8 g of chloride-intercalated nickel-manganese-based hydrotalcite (as a chloride-selective barrier material with Q0 / Q1 of 0.997 and I0 / I1 of 0.997), 108 g of 5% Nafion solution, and 104 g of ethylene glycol aqueous solution (obtained by mixing ethylene glycol and water at a volume ratio of 3:1). This slurry was then coated onto the membrane side carrying the cathode catalytic layer and hot-pressed at 300 °C and 10 MPa for 5 min to form a chloride-selective barrier material layer on the cathode surface. The chloride-selective barrier material loading in the chloride-selective barrier material layer was 6 mg / cm³. 2 The chloride ion selective barrier material layer has a thickness of 75 micrometers, a total nickel-manganese content of 78 wt%, a chloride ion content of 4.2 wt%, and a nickel-manganese molar ratio of 4:1. It has a layered structure with an average lateral dimension of 720 nm, an average longitudinal dimension of 28 nm, and a specific surface area of ​​126 m². 2 / g, pore volume 0.45cm 3 / g, with an average pore size of 5.5nm and an interlayer spacing d(003) of 0.84nm.

[0107] The method for manufacturing the chloride ion intercalated nickel-manganese-based hydrotalcite@nitrogen-modified carbon core-shell catalyst is as follows: 833g of nickel chloride, 208g of manganese chloride, 4.2kg of urea and 434g of potassium chloride are placed in a 70L reactor and stirred evenly. The mixture is reacted at 200℃ for 6h. After washing and drying, chloride ion modified nickel-manganese hydrotalcite is obtained. It is then placed in 55.6g of resorcinol, 25L of formaldehyde, 18L of ethylenediamine and 6L of ethanol aqueous solution (the volume ratio of water to ethanol is 7:3) and stirred at 25℃ for 20h. After calcination at 800℃ for 5h under a nitrogen atmosphere, chloride ion intercalated hydrotalcite@nitrogen-modified carbon core-shell catalyst is obtained.

[0108] (4) The materials obtained above are assembled into an electrolytic cell, and seawater is used as the water source. A 22wt% sodium hydroxide seawater solution is prepared as the electrolyte, which contains chloride ions (Cl... 1- The content of [missing information] was 2.5 wt%, the current efficiency Y was 99.7%, Y' was 99.6%, and after 200 h of reaction, the Cl in the electrolyte was 63300 mg / L. At this time, C0 / C1 was 1.283, Y' / Y was 0.997, C0' / C1' was 0.51, and Y1' / Y1 was 0.998. Electrolysis was started under these conditions, with an operating temperature of 70℃, an operating pressure of 1.6 MPaG, and an operating chamber voltage of 2.0 V. The performance evaluation results are shown in Table 1.

[0109] Example 4

[0110] The preparation, assembly, and electrolysis methods of the electrolysis device are the same as in Example 1, except that an alkaline seawater solution containing 10 wt% sodium hydroxide is prepared, at which point the CO / C1 ratio is 1.1.

[0111] Example 5

[0112] (1) 4.7 g of nickel-molybdenum alloy cathode catalyst (nickel-molybdenum atomic ratio of 5:1) and 27 g of 5% Nafion solution were added to 104 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) and ultrasonically mixed to prepare a cathode slurry. This slurry was then coated onto one side of a 25*25 cm anion exchange membrane and subjected to hot-pressing. The hot-pressing conditions included a temperature of 150℃, a pressure of 3 MPa, and a time of 20 min to form a cathode on one side of the exchange membrane. The cathode catalyst loading in the cathode was 7.5 mg / cm³. 2 The cathode thickness is 83 micrometers.

[0113] (2) The anion exchange membrane is of model Versogen A80, and its functional group is a dimethylpiperidine ion functional group. The thickness of the exchange membrane is 80 micrometers.

[0114] (3) 2.5g of chloride-intercalated nickel-iron-based hydrotalcite (as a chloride-selective barrier material, Q0 / Q1 = 0.995, I0 / I1 = 0.995) and 38g of 5% Nafion solution were added to 88g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) to prepare a chloride-selective barrier material slurry. This slurry was coated onto the cathode and hot-pressed at 200℃ and 15MPa for 1 min to form a chloride-selective barrier material layer on the cathode surface. The chloride-selective barrier material loading in the chloride-selective barrier material layer was 4mg / cm³. 2 The chloride ion selective barrier material layer has a thickness of 42 micrometers, a total nickel-iron content of 80 wt%, a chloride ion content of 3.5 wt%, and a nickel-iron molar ratio of 5:1. It has a layered structure with an average lateral dimension of 650 nm, an average longitudinal dimension of 22 nm, and a specific surface area of ​​140 m². 2 / g, pore volume 0.42cm 3 / g, with an average pore size of 5.2nm and an interlayer spacing d(003) of 0.8nm.

[0115] The method for manufacturing the chloride ion intercalated nickel-iron-based hydrotalcite@nitrogen-modified carbon core-shell catalyst is as follows: 700g of nickel nitrate, 139g of ferric nitrate, 1.6kg of urea and 278g of sodium chloride are placed in a 1L reactor and stirred evenly. The mixture is reacted at 150℃ for 6h. After washing and drying, chloride ion-modified nickel-iron hydrotalcite is obtained. This hydrotalcite is then placed in 28g of resorcinol, 14L of formaldehyde, 11L of ethylenediamine and 3L of ethanol aqueous solution (the volume ratio of water to ethanol is 7:3) and stirred at 25℃ for 24h. Finally, it is calcined at 700℃ for 6h under an ammonia atmosphere to obtain the chloride ion intercalated hydrotalcite@nitrogen-modified carbon core-shell catalyst.

[0116] (4) An anode slurry was prepared by mixing 5.3 g of cobalt-manganese-based anode catalyst (specifically cobalt-manganese phosphide, with a cobalt-manganese atomic ratio of 3:1 and a phosphorus content of 5.5 wt%), 84 g of 5% Nafion solution, and 60 g of isopropanol. The anode slurry was coated onto the other side of the exchange membrane a material and subjected to hot pressing. The hot pressing conditions included a temperature of 120°C, a pressure of 6 MPa, and a time of 20 min to form an anode with a thickness of 100 micrometers. The loading of the anode catalyst in the anode was 8.5 mg / cm³. 2 Finally, an electrolysis chamber is obtained, the structure of which is shown in Figure 1. From left to right, it includes an anode, an exchange membrane, a cathode, and a chloride ion selective barrier material layer.

[0117] (5) Pass the obtained electrolysis device into seawater. Using seawater as the water source, prepare a 20wt% sodium hydroxide seawater solution as the electrolyte, whose chloride ion (Cl) 1- The content of [missing information] was 1.7 wt%, the current efficiency Y was 99.7%, Y′ was 99.6%, and after 200 h of reaction, the Cl in the electrolyte was 43000 mg / L. At this time, C0 / C1 was 1.26, Y′ / Y was 0.997, C0' / C1′ was 0.49, and Y1′ / Y1 was 0.992. Electrolysis was started under these conditions, with an operating temperature of 70℃, an operating pressure of 1.6 MPaG, and an operating chamber voltage of 2.0 V. The performance evaluation results are shown in Table 1.

[0118] The preparation, assembly, and electrolysis methods of the electrolysis device are the same as in Example 1, where Y′ / Y is 0.992.

[0119] Example 6

[0120] The preparation, assembly, and electrolysis methods of the electrolysis device are the same as in Example 1, except that the byproduct precipitation operation is started after the electrolyte balance control process is adjusted so that the concentration reaches 30000 mg / L. At this time, CO' / C1' is 0.71.

[0121] Example 7

[0122] (1) 4.4 g of nickel-molybdenum alloy cathode catalyst (nickel-molybdenum atomic ratio of 6:1) and 26 g of 5% Nafion solution were added to 104 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) and ultrasonically mixed to form a cathode slurry. This slurry was then coated onto one side of a 25*25 cm anion exchange membrane and subjected to hot pressing. The hot pressing conditions included a temperature of 120℃, a pressure of 5 MPa, and a time of 15 min to form a cathode on one side of the exchange membrane. The cathode catalyst loading in the cathode was 7 mg / cm³. 2 The cathode thickness is 80 micrometers.

[0123] (2) The anion exchange membrane is of model Versogen A80, and its functional group is a dimethylpiperidine ion functional group. The thickness of the exchange membrane is 80 micrometers.

[0124] (3) A directional selective catalytic slurry was prepared by uniformly mixing 2.8 g of chloride ion intercalated nickel-manganese-based hydrotalcite (as a chloride ion selective blocking material, with Q0 / Q1 of 0.996 and I0 / I1 of 0.996), 97 g of 5% Nafion solution, and 90 g of ethylene glycol aqueous solution (obtained by mixing ethylene glycol and water at a volume ratio of 3:1). This slurry was then coated onto the membrane side carrying the cathode catalytic layer and hot-pressed at 350 °C and 15 MPa for 3 min to form a chloride ion selective blocking material layer on the cathode surface. The chloride ion selective blocking material loading in the chloride ion selective blocking material layer was 4.5 mg / cm³. 2 The chloride ion selective barrier material layer has a thickness of 48 micrometers, a total nickel-manganese content of 80 wt%, a chloride ion content of 3.9 wt%, and a nickel-manganese molar ratio of 4:1. It has a layered structure with an average lateral dimension of 760 nm, an average longitudinal dimension of 30 nm, and a specific surface area of ​​127 m². 2 / g, pore volume 0.45cm 3 / g, with an average pore size of 5.5nm and an interlayer spacing d(003) of 0.85nm.

[0125] The method for manufacturing the chloride ion intercalated nickel-manganese-based hydrotalcite@nitrogen-modified carbon core-shell catalyst is as follows: 868g of nickel chloride, 180g of manganese chloride, 4.5kg of urea and 300g of potassium chloride are placed in a 70L reactor and stirred evenly. The mixture is reacted at 180℃ for 12h. After washing and drying, chloride ion modified nickel-manganese hydrotalcite is obtained. The hydrotalcite is then placed in 56g of resorcinol, 25L of formaldehyde, 16L of ethylenediamine and 5.5L of ethanol aqueous solution (the volume ratio of water to ethanol is 7:3) and stirred at 25℃ for 20h. After calcination at 750℃ for 5h under a nitrogen atmosphere, chloride ion intercalated hydrotalcite@nitrogen-modified carbon core-shell catalyst is obtained.

[0126] (4) Prepare an anode slurry by mixing 5g of cobalt-manganese-based anode catalyst (specifically cobalt-manganese selenide, with a cobalt-manganese atomic ratio of 3:1 and a selenium content of 3wt%), 83g of 5% Nafion solution, and 60g of isopropanol. Coat the anode slurry onto the other side of the exchange membrane a material and perform hot-pressing treatment. The hot-pressing conditions include: temperature of 180℃, pressure of 12MPa, and time of 20min, to form an anode with a thickness of 96 micrometers. The loading of the anode catalyst in the anode is 8.5mg / cm³. 2 Finally, an electrolysis chamber is obtained, the structure of which is shown in Figure 1. From left to right, it includes an anode, an exchange membrane, a cathode, and a chloride ion selective barrier material layer.

[0127] (5) Pass the electrolysis device obtained in (4) into seawater. Using seawater as the water source, prepare a 20wt% sodium hydroxide seawater solution as the electrolyte, whose chloride ion (Cl) 1- The content of [missing information] was 1.7 wt%, the current efficiency Y was 99.7%, Y′ was 99.6%, and after 200 h of reaction, the Cl in the electrolyte was 43000 mg / L. At this time, C0 / C1 was 1.26, Y′ / Y was 0.997, C0' / C1′ was 0.49, and Y1′ / Y1 was 0.993. Electrolysis was started under these conditions, with an operating temperature of 70℃, an operating pressure of 1.6 MPaG, and an operating chamber voltage of 2.0 V. The performance evaluation results are shown in Table 1.

[0128] The preparation, assembly, and electrolysis methods of the electrolysis device are the same as in Example 1, where Y1' / Y1 is 0.993.

[0129] Example 8

[0130] The preparation, assembly and electrolysis methods of the electrolysis device are the same as in Example 1, except that the treated water first comes into contact with the anode, that is, the chloride ion selective barrier material is set on the outside of the anode.

[0131] Example 9

[0132] The preparation, assembly and electrolysis methods of the electrolysis device are the same as in Example 1, except that: the chloride ion selective barrier material is loaded into the seawater pretreatment tank and then brought into contact with the electrode, that is, it is not a zero-gap method.

[0133] Example 10

[0134] The preparation, assembly, and electrolysis methods of the electrolysis device are the same as in Example 1, except that the loading of the chloride ion selective blocking material is 0.4 mg / cm³. 2 .

[0135] Example 11

[0136] (1) 4.4 g of nickel-molybdenum alloy cathode catalyst (nickel-molybdenum atomic ratio of 6:1) and 26 g of 5% Nafion solution were added to 104 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) and ultrasonically mixed to form a cathode slurry. This slurry was then coated onto one side of a 25*25 cm anion exchange membrane and subjected to hot pressing. The hot pressing conditions included a temperature of 120℃, a pressure of 5 MPa, and a time of 15 min to form a cathode on one side of the exchange membrane. The cathode catalyst loading in the cathode was 7 mg / cm³. 2 The cathode thickness is 80 micrometers.

[0137] (2) An anion exchange membrane that allows water and anions to pass through, the functional group of which is a dimethylpiperidine ion functional group, the model of which is Versogen A80, and the thickness of the exchange membrane is 80 micrometers.

[0138] (3) 3g of nickel-iron-based sulfide (as a chloride ion selective blocking material, Q0 / Q1 = 0.996, I0 / I1 = 0.996) and 33g of 5% Nafion solution were added to 87.5g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) to prepare a chloride ion selective blocking material slurry. This slurry was coated onto the cathode and hot-pressed at 200℃ and 15MPa for 1min to form a chloride ion selective blocking material layer on the cathode surface. The chloride ion selective blocking material loading in the chloride ion selective blocking material layer was 4.7mg / cm³. 2 The chloride ion selective barrier material layer has a thickness of 50 micrometers, a total nickel-iron content of 80 wt%, a sulfur ion content of 3.5 wt%, and a nickel-iron molar ratio of 4:1. It has a layered structure with an average lateral dimension of 600 nm, an average longitudinal dimension of 22 nm, and a specific surface area of ​​140 m². 2 / g, pore volume 0.42cm 3 / g, with an average pore size of 5.0nm.

[0139] The method for manufacturing the nickel-iron-based sulfide@nitrogen-modified carbon core-shell catalyst is as follows: 1 kg of nickel nitrate, 277 g of iron nitrate, and 2.2 kg of urea are placed in a 70 L reactor and stirred evenly. The mixture is reacted at 150 °C for 6 h. After washing and drying, an intermediate powder is obtained. The intermediate powder is transferred to a 0.2 mol / L thiourea solution and reacted at 160 °C for 10 h. After washing and drying, a nickel-iron-based sulfide is obtained. This sulfide is then placed in a solution of 28 g of resorcinol, 2 L of formaldehyde, 10 L of ethylenediamine, and 2.7 L of an aqueous ethanol solution (water to ethanol volume ratio of 7:3). The solution is stirred at 25 °C for 24 h and then calcined at 600 °C for 10 h under an ammonia atmosphere to obtain the nickel-iron-based sulfide@nitrogen-modified carbon core-shell catalyst.

[0140] (4) An anode slurry was prepared by mixing 5.3 g of cobalt-manganese-based anode catalyst (specifically cobalt-manganese phosphide, with a cobalt-manganese atomic ratio of 3:1 and a phosphorus content of 5.5 wt%), 83 g of 5% Nafion solution, and 59 g of isopropanol. The anode slurry was coated onto the other side of the exchange membrane a material and subjected to hot pressing. The hot pressing conditions included a temperature of 120°C, a pressure of 6 MPa, and a time of 20 min to form an anode with a thickness of 100 micrometers. The loading of the anode catalyst in the anode was 8.5 mg / cm³. 2 Finally, an electrolysis chamber is obtained, the structure of which is shown in Figure 1. From left to right, it includes an anode, an exchange membrane, a cathode, and a chloride ion selective barrier material layer.

[0141] (5) Pass the electrolysis device obtained in (4) into seawater. Using seawater as the water source, prepare a 20wt% sodium hydroxide seawater solution as the electrolyte, whose chloride ions (Cl) 1- The content of [missing information] was 1.7 wt%, the current efficiency Y was 99.7%, Y' was 99.6%, and after 200 h of reaction, the Cl in the electrolyte was 43000 mg / L. At this time, C0 / C1 was 1.26, Y' / Y was 0.999, C0' / C1′ was 0.50, and Y1' / Y1 was 0.998. Electrolysis was started under these conditions, with an operating temperature of 70℃, an operating pressure of 1.6 MPaG, and an operating chamber voltage of 2.0 V. The performance evaluation results are shown in Table 1.

[0142] The preparation, assembly, and electrolysis methods of the electrolysis device are the same as in Example 1, except that the chloride ion selective blocking material is nickel-iron sulfide (where the nickel-iron atomic ratio is 5:1 and the sulfur content is 4.8 wt%).

[0143] Example 12

[0144] (1) 4.4 g of nickel-molybdenum alloy cathode catalyst (nickel-molybdenum atomic ratio of 6:1) and 26 g of 5% Nafion solution were added to 105 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) and ultrasonically mixed to prepare a cathode slurry. This slurry was then coated onto one side of a 25*25 cm anion exchange membrane and subjected to hot pressing. The hot pressing conditions included a temperature of 120℃, a pressure of 5 MPa, and a time of 15 min to form a cathode on one side of the exchange membrane. The cathode catalyst loading in the cathode was 7 mg / cm³. 2 The cathode thickness is 80 micrometers.

[0145] (2) The anion exchange membrane is of model Versogen A80, and its functional group is a dimethylpiperidine ion functional group. The thickness of the exchange membrane is 80 micrometers.

[0146] (3) 3.1 mg of chloride-intercalated cobalt-manganese-based hydrotalcite (as a chloride ion selective blocking material, Q0 / Q1 = 0.998, I0 / I1 = 0.998) and 38 g of 5% Nafion solution were added to 88 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) to prepare a chloride ion selective blocking material slurry. This slurry was coated onto the cathode and hot-pressed at 200℃ and 15 MPa for 1 min to form a chloride ion selective blocking material layer on the cathode surface. The chloride ion selective blocking material loading in the chloride ion selective blocking material layer was 5 mg / cm³. 2 The chloride ion selective barrier material layer has a thickness of 50 micrometers, a total cobalt and manganese content of 84 wt%, a chloride ion content of 4.0 wt%, and a cobalt-manganese molar ratio of 5:1. It has a layered structure with an average lateral dimension of 650 nm, an average longitudinal dimension of 22 nm, and a specific surface area of ​​140 m². 2 / g, pore volume 0.42cm 3 / g, with an average pore size of 5.2nm and an interlayer spacing d(003) of 0.81nm.

[0147] The method for manufacturing the chloride ion intercalated cobalt-manganese-based hydrotalcite@nitrogen-modified carbon core-shell catalyst is as follows: 833g of cobalt nitrate, 140g of manganese nitrate, 2.4kg of urea and 486g of sodium chloride are placed in a 70L reactor and stirred evenly. The mixture is reacted at 180℃ for 6h. After washing and drying, chloride ion-modified cobalt-manganese hydrotalcite is obtained. This hydrotalcite is then placed in 28g of resorcinol, 14L of formaldehyde, 11L of ethylenediamine and 3L of ethanol aqueous solution (the volume ratio of water to ethanol is 7:3) and stirred at 25℃ for 24h. Finally, it is calcined at 600℃ for 10h under an ammonia atmosphere to obtain the chloride ion intercalated hydrotalcite@nitrogen-modified carbon core-shell catalyst.

[0148] (4) An anode slurry was prepared by mixing 5.3 g of cobalt-manganese-based anode catalyst (specifically cobalt-manganese phosphide, with a cobalt-manganese atomic ratio of 3:1 and a phosphorus content of 5.5 wt%), 83 g of 5% Nafion solution, and 59 g of isopropanol. The anode slurry was coated onto the other side of the exchange membrane a material and subjected to hot pressing. The hot pressing conditions included a temperature of 120°C, a pressure of 6 MPa, and a time of 20 min to form an anode with a thickness of 100 micrometers. The loading of the anode catalyst in the anode was 8.5 mg / cm³. 2 Finally, an electrolysis chamber is obtained, the structure of which is shown in Figure 1. From left to right, it includes an anode, an exchange membrane, a cathode, and a chloride ion selective barrier material layer.

[0149] (5) Pass the electrolysis device obtained in (4) into seawater. Using seawater as the water source, prepare a 20wt% sodium hydroxide seawater solution as the electrolyte, whose chloride ions (Cl) 1-The content of [missing information] was 1.7 wt%, the current efficiency Y was 99.7%, Y' was 99.6%, and after 200 h of reaction, the Cl in the electrolyte was 43000 mg / L. At this time, C0 / C1 was 1.26, Y' / Y was 0.999, C0' / C1′ was 0.50, and Y1' / Y1 was 0.998. Electrolysis was started under these conditions, with an operating temperature of 70℃, an operating pressure of 1.6 MPaG, and an operating chamber voltage of 2.0 V. The performance evaluation results are shown in Table 1.

[0150] The preparation, assembly and electrolysis methods of the electrolysis device are the same as in Example 1, except that the chloride ion selective blocking material is chloride ion intercalated cobalt-manganese-based hydrotalcite.

[0151] Example 13

[0152] (1) 4.4 g of nickel-molybdenum alloy cathode catalyst (nickel-molybdenum atomic ratio of 6:1) and 26 g of 5% Nafion solution were added to 104 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) and ultrasonically mixed to form a cathode slurry. This slurry was then coated onto one side of a 25*25 cm anion exchange membrane and subjected to hot pressing. The hot pressing conditions included a temperature of 120℃, a pressure of 5 MPa, and a time of 15 min to form a cathode on one side of the exchange membrane. The cathode catalyst loading in the cathode was 7 mg / cm³. 2 The cathode thickness is 80 micrometers.

[0153] (2) The anion exchange membrane is of model Versogen A80, and its functional group is a dimethylpiperidine ion functional group. The thickness of the exchange membrane is 80 micrometers.

[0154] (3) 45 mg of carbonate ion-intercalated nickel-iron-based hydrotalcite (as a chloride ion selective blocking material, Q0 / Q1 = 0.998, I0 / I1 = 0.998) and 38 g of 5% Nafion solution were added to 88 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) to prepare a chloride ion selective blocking material slurry. This slurry was coated onto the cathode and hot-pressed at 200℃ and 15 MPa for 1 min to form a chloride ion selective blocking material layer on the cathode surface. The chloride ion selective blocking material loading in the chloride ion selective blocking material layer was 5 mg / cm³. 2 The chloride ion selective barrier material layer has a thickness of 50 micrometers, a total nickel-iron content of 80 wt%, a carbonate ion content of 3.4 wt%, and a nickel-iron molar ratio of 5:1. It has a layered structure with an average lateral dimension of 650 nm, an average longitudinal dimension of 22 nm, and a specific surface area of ​​140 m². 2 / g, pore volume 0.42cm 3 / g, with an average pore size of 5.2nm and an interlayer spacing d(003) of 0.76nm.

[0155] The method for manufacturing the carbonate ion-intercalated nickel-iron-based hydrotalcite@nitrogen-modified carbon core-shell catalyst is as follows: 695g of nickel nitrate, 174g of ferric nitrate, and 2.1kg of urea are placed in a 70L reactor and stirred evenly. The mixture is reacted at 150℃ for 6h. After washing and drying, chloride-modified nickel-iron hydrotalcite is obtained. This hydrotalcite is then placed in 28g of resorcinol, 14L of formaldehyde, 11L of ethylenediamine, and 2.8L of an aqueous ethanol solution (water to ethanol volume ratio of 7:3) and stirred at 25℃ for 24h. Finally, it is calcined at 600℃ for 10h under an ammonia atmosphere to obtain the chloride ion-intercalated hydrotalcite@nitrogen-modified carbon core-shell catalyst.

[0156] (4) An anode slurry was prepared by mixing 5.3 g of cobalt-manganese-based anode catalyst (specifically cobalt-manganese phosphide, with a cobalt-manganese atomic ratio of 3:1 and a phosphorus content of 5.5 wt%), 83 g of 5% Nafion solution, and 59 g of isopropanol. The anode slurry was coated onto the other side of the exchange membrane a material and subjected to hot pressing. The hot pressing conditions included a temperature of 120°C, a pressure of 6 MPa, and a time of 20 min to form an anode with a thickness of 100 micrometers. The loading of the anode catalyst in the anode was 8.5 mg / cm³. 2 Finally, an electrolysis chamber is obtained, the structure of which is shown in Figure 1. From left to right, it includes an anode, an exchange membrane, a cathode, and a chloride ion selective barrier material layer.

[0157] (5) Pass the electrolysis device obtained in (4) into seawater. Using seawater as the water source, prepare a 20wt% sodium hydroxide seawater solution as the electrolyte, whose chloride ions (Cl) 1- The content of [missing information] was 1.7 wt%, the current efficiency Y was 99.7%, Y′ was 99.6%, and after 200 h of reaction, the Cl in the electrolyte was 43000 mg / L. At this point, C0 / C1 was 1.26, Y′ / Y was 0.999, C0' / C1′ was 0.50, and Y1′ / Y1 was 0.998. Electrolysis was started under these conditions: operating temperature 70℃, operating pressure 1.6 MPaG, and operating chamber voltage 2.0 V. The performance evaluation results are shown in Table 1.

[0158] The preparation, assembly, and electrolysis methods of the electrolysis device are the same as in Example 1, except that the anion is carbonate ion.

[0159] Example 14

[0160] (1) 4.4 g of nickel-molybdenum alloy cathode catalyst (nickel-molybdenum atomic ratio of 6:1) and 26 g of 5% Nafion solution were added to 104 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) and ultrasonically mixed to form a cathode slurry. This slurry was then coated onto one side of a 25*25 cm anion exchange membrane and subjected to hot pressing. The hot pressing conditions included a temperature of 120℃, a pressure of 5 MPa, and a time of 15 min to form a cathode on one side of the exchange membrane. The cathode catalyst loading in the cathode was 7 mg / cm³. 2 The cathode thickness is 80 micrometers.

[0161] (2) The anion exchange membrane is of model Versogen A80, and its functional group is a dimethylpiperidine ion functional group. The thickness of the exchange membrane is 80 micrometers.

[0162] (3) 3.2g of chloride-intercalated nickel-iron-based hydrotalcite (as a chloride-selective barrier material, Q0 / Q1 = 0.998, I0 / I1 = 0.998) and 38g of 5% Nafion solution were added to 88g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) to prepare a chloride-selective barrier material slurry. This slurry was coated onto the cathode and hot-pressed at 200℃ and 15MPa for 1min to form a chloride-selective barrier material layer on the cathode surface. The chloride-selective barrier material A1 loading in the chloride-selective barrier material layer was 5mg / cm³. 2 The chloride ion selective barrier material layer has a thickness of 50 micrometers, a total nickel-iron content of 80 wt%, a chloride ion content of 4.0 wt%, and a nickel-iron molar ratio of 5:1. It has a layered structure with an average lateral dimension of 650 nm, an average longitudinal dimension of 22 nm, and a specific surface area of ​​140 m². 2 / g, pore volume 0.42cm 3 / g, with an average pore size of 5.2nm and an interlayer spacing d(003) of 0.8nm.

[0163] The method for manufacturing the chloride ion intercalated nickel-iron-based hydrotalcite@nitrogen-modified carbon core-shell catalyst is as follows: 694g of nickel nitrate, 174g of ferric nitrate, 1.7kg of urea and 181g of sodium chloride are placed in a 70L reactor and stirred evenly. The mixture is reacted at 140℃ for 4h. After washing and drying, chloride ion-modified nickel-iron hydrotalcite is obtained. This hydrotalcite is then placed in 28g of resorcinol, 14L of formaldehyde, 11L of ethylenediamine and 3L of ethanol aqueous solution (the volume ratio of water to ethanol is 7:3) and stirred at 25℃ for 24h. Finally, it is calcined at 600℃ for 10h under an ammonia atmosphere to obtain the chloride ion intercalated hydrotalcite@nitrogen-modified carbon core-shell catalyst.

[0164] (4) An anode slurry was prepared by mixing 5.3g of cobalt-manganese-based anode catalyst (specifically cobalt-manganese phosphide, with a cobalt-manganese atomic ratio of 3:1 and a phosphorus content of 5.5wt%), 83g of 5% Nafion solution, and 60g of isopropanol. The anode slurry was coated onto the other side of the exchange membrane a material and subjected to hot pressing. The hot pressing conditions included a temperature of 120°C, a pressure of 6MPa, and a time of 20min to form an anode with a thickness of 100 micrometers. The loading of the anode catalyst in the anode was 8.5mg / cm³. 2 Finally, an electrolysis chamber is obtained, the structure of which is shown in Figure 1. From left to right, it includes an anode, an exchange membrane, a cathode, and a chloride ion selective barrier material layer.

[0165] (5) Pass the electrolysis device obtained in (4) into seawater. Using seawater as the water source, prepare a 20wt% sodium hydroxide seawater solution as the electrolyte, whose chloride ions (Cl) 1- The content of [missing information] was 1.7 wt%, the current efficiency Y was 99.7%, Y′ was 99.6%, and after 200 h of reaction, the Cl in the electrolyte was 43000 mg / L. At this point, C0 / C1 was 1.26, Y′ / Y was 0.999, C0' / C1′ was 0.50, and Y1′ / Y1 was 0.998. Electrolysis was started under these conditions: operating temperature 70℃, operating pressure 1.6 MPaG, and operating chamber voltage 2.0 V. The performance evaluation results are shown in Table 1.

[0166] The preparation, assembly, and electrolysis methods of the electrolysis device are the same as in Example 1, except that the chloride ion content is 1.5%.

[0167] Example 15

[0168] (1) 4.4 g of nickel-molybdenum alloy cathode catalyst (nickel-molybdenum atomic ratio of 6:1) and 26 g of 5% Nafion solution were added to 104 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) and ultrasonically mixed to form a cathode slurry. This slurry was then coated onto one side of a 25*25 cm anion exchange membrane and subjected to hot pressing. The hot pressing conditions included a temperature of 120℃, a pressure of 5 MPa, and a time of 15 min to form a cathode on one side of the exchange membrane. The cathode catalyst loading in the cathode was 7 mg / cm³. 2 The cathode thickness is 80 micrometers.

[0169] (2) The anion exchange membrane is of model Versogen A80, and its functional group is a dimethylpiperidine ion functional group. The thickness of the exchange membrane is 80 micrometers.

[0170] (3) 3.2 mg of chloride-intercalated nickel-iron-based hydrotalcite (as a chloride-selective barrier material, Q0 / Q1 = 0.998, I0 / I1 = 0.998) and 38 g of 5% Nafion solution were added to 88 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) to prepare a chloride-selective barrier material slurry. This slurry was coated onto the cathode and hot-pressed at 200℃ and 15 MPa for 1 min to form a chloride-selective barrier material layer on the cathode surface. The chloride-selective barrier material A1 loading in the chloride-selective barrier material layer was 5 mg / cm³. 2 The chloride ion selective barrier material layer has a thickness of 50 micrometers, a total nickel-iron content of 80 wt%, a chloride ion content of 4.0 wt%, and a nickel-iron molar ratio of 5:1. It has a layered structure with an average lateral dimension of 650 nm, an average longitudinal dimension of 22 nm, and a specific surface area of ​​140 m². 2 / g, pore volume 0.42cm 3 / g, with an average pore size of 5.2nm and an interlayer spacing d(003) of 0.8nm.

[0171] The method for manufacturing the chloride ion intercalated nickel-iron-based layered double hydroxide (LDH)@nitrogen-modified carbon core-shell catalyst is as follows: 694g of nickel nitrate, 174g of ferric nitrate, 1.7g of urea, and 833g of sodium chloride are placed in a 70L reactor and stirred evenly. The mixture is reacted at 180℃ for 24h. After washing and drying, chloride ion-modified nickel-iron LDH is obtained. The LDH is then placed in 28g of resorcinol, 14L of formaldehyde, 11L of ethylenediamine, and 2.8L of an aqueous ethanol solution (water to ethanol volume ratio of 7:3) and stirred at 25℃ for 24h. Finally, the mixture is calcined at 600℃ for 10h under an ammonia atmosphere to obtain the chloride ion intercalated LDH@nitrogen-modified carbon core-shell catalyst.

[0172] (4) An anode slurry was prepared by mixing 5.3 g of cobalt-manganese-based anode catalyst (specifically cobalt-manganese phosphide, with a cobalt-manganese atomic ratio of 3:1 and a phosphorus content of 5.5 wt%), 83 g of 5% Nafion solution, and 59 g of isopropanol. The anode slurry was coated onto the other side of the exchange membrane material and subjected to hot-pressing. The hot-pressing conditions included a temperature of 120°C, a pressure of 6 MPa, and a time of 20 min to form an anode with a thickness of 100 micrometers. The loading of the anode catalyst in the anode was 8.5 mg / cm³. 2 Finally, an electrolysis chamber is obtained, the structure of which is shown in Figure 1. From left to right, it includes an anode, an exchange membrane, a cathode, and a chloride ion selective barrier material layer.

[0173] (5) Pass the electrolysis device obtained in (4) into seawater. Using seawater as the water source, prepare a 20wt% sodium hydroxide seawater solution as the electrolyte, whose chloride ions (Cl) 1-The content of [missing information] was 1.7 wt%, the current efficiency Y was 99.7%, Y′ was 99.6%, and after 200 h of reaction, the Cl in the electrolyte was 43000 mg / L. At this point, C0 / C1 was 1.26, Y′ / Y was 0.999, C0' / C1′ was 0.50, and Y1′ / Y1 was 0.998. Electrolysis was started under these conditions: operating temperature 70℃, operating pressure 1.6 MPaG, and operating chamber voltage 2.0 V. The performance evaluation results are shown in Table 1.

[0174] The preparation, assembly, and electrolysis methods of the electrolysis device are the same as in Example 1, except that the chloride ion content is 6%.

[0175] Example 16

[0176] (1) 4.4 g of nickel-molybdenum alloy cathode catalyst (nickel-molybdenum atomic ratio of 6:1) and 378 mg of 5% Nafion solution were added to 104 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) and ultrasonically mixed to prepare a cathode slurry. This slurry was then coated onto one side of a 25*25 cm anion exchange membrane and subjected to hot pressing. The hot pressing conditions included a temperature of 120℃, a pressure of 5 MPa, and a time of 15 min to form a cathode on one side of the exchange membrane. The cathode catalyst loading in the cathode was 7 mg / cm³. 2 The cathode thickness is 80 micrometers.

[0177] (2) The anion exchange membrane is of model Versogen A80, and its functional group is a dimethylpiperidine ion functional group. The thickness of the exchange membrane is 80 micrometers.

[0178] (3) A chloride ion selectively blocking material slurry was prepared by adding 2.7g of chloride ion intercalated nickel-iron-based hydrotalcite (as a chloride ion selective blocking material, Q0 / Q1 = 0.98, I0 / I1 = 0.98) and 38g of 5% Nafion solution to 88g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1). This slurry was coated onto the cathode and hot-pressed at 280℃ and 15MPa for 8min to form a chloride ion selectively blocking material layer on the cathode surface. The chloride ion selectively blocking material loading in the layer was 4.2mg / cm³. 2 The chloride ion selective barrier material layer has a thickness of 42 micrometers, a total nickel-iron content of 80 wt%, a chloride ion content of 3.6 wt%, and a nickel-iron molar ratio of 6:1. It has a layered structure with an average lateral dimension of 800 nm, an average longitudinal dimension of 28 nm, and a specific surface area of ​​122 m². 2 / g, pore volume is 0.46cm 3 / g, with an average pore size of 5.4nm and an interlayer spacing d(003) of 0.83nm.

[0179] The method for manufacturing the chloride ion intercalated nickel-iron-based hydrotalcite@nitrogen-modified carbon core-shell catalyst is as follows: 1.1g of nickel nitrate, 174g of ferric nitrate, 1.9kg of urea and 396g of sodium chloride are placed in a 70L reactor and stirred evenly. The mixture is reacted at 140℃ for 8h. After washing and drying, chloride ion-modified nickel-iron hydrotalcite is obtained. This hydrotalcite is then placed in 28g of resorcinol, 14L of formaldehyde, 11L of ethylenediamine and 2.8L of an aqueous ethanol solution (water to ethanol volume ratio of 7:3) and stirred at 25℃ for 24h. Finally, it is calcined at 600℃ for 10h under an ammonia atmosphere to obtain the chloride ion intercalated hydrotalcite@nitrogen-modified carbon core-shell catalyst.

[0180] (4) An anode slurry was prepared by mixing 5.3 g of cobalt-manganese-based anode catalyst (specifically cobalt-manganese phosphide, with a cobalt-manganese atomic ratio of 3:1 and a phosphorus content of 5.5 wt%), 83 g of 5% Nafion solution, and 59 g of isopropanol. The anode slurry was coated onto the other side of the exchange membrane a material and subjected to hot pressing. The hot pressing conditions included a temperature of 120°C, a pressure of 6 MPa, and a time of 20 min to form an anode with a thickness of 100 micrometers. The loading of the anode catalyst in the anode was 8.5 mg / cm³. 2 Finally, an electrolysis chamber is obtained, the structure of which is shown in Figure 1. From left to right, it includes an anode, an exchange membrane, a cathode, and a chloride ion selective barrier material layer.

[0181] (5) Pass the electrolysis device obtained in (4) into seawater. Using seawater as the water source, prepare a 20wt% sodium hydroxide seawater solution as the electrolyte, whose chloride ions (Cl) 1- The content of [missing information] was 1.7 wt%, the current efficiency Y was 99.7%, Y′ was 99.6%, and after 200 h of reaction, the Cl in the electrolyte was 43000 mg / L. At this point, C0 / C1 was 1.26, Y′ / Y was 0.999, C0' / C1′ was 0.50, and Y1′ / Y1 was 0.998. Electrolysis was started under these conditions: operating temperature 70℃, operating pressure 1.6 MPaG, and operating chamber voltage 2.0 V. The performance evaluation results are shown in Table 1.

[0182] The preparation, assembly, and electrolysis methods of the electrolysis device are the same as in Example 1, except that Q0 / Q1 is 0.98 and I0 / I1 is 0.98.

[0183] Example 17

[0184] (1) 4.4 g of nickel-molybdenum alloy cathode catalyst (nickel-molybdenum atomic ratio of 6:1) and 26 g of 5% Nafion solution were added to 104 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) and ultrasonically mixed to form a cathode slurry. This slurry was then coated onto one side of a 25*25 cm anion exchange membrane and subjected to hot pressing. The hot pressing conditions included a temperature of 120℃, a pressure of 5 MPa, and a time of 15 min to form a cathode on one side of the exchange membrane. The cathode catalyst loading in the cathode was 7 mg / cm³. 2 The cathode thickness is 80 micrometers.

[0185] (2) The anion exchange membrane is of model Versogen A80, and its functional group is a dimethylpiperidine ion functional group. The thickness of the exchange membrane is 80 micrometers.

[0186] (3) 3g of chloride-intercalated nickel-cobalt-based hydrotalcite (as a chloride-selective barrier material, Q0 / Q1 = 0.985, I0 / I1 = 0.985) and 38g of 5% Nafion solution were added to 88g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) to prepare a chloride-selective barrier material slurry. This slurry was coated onto the cathode and hot-pressed at 200℃ and 15MPa for 1min to form a chloride-selective barrier material layer on the cathode surface. The chloride-selective barrier material loading in the chloride-selective barrier material layer was 5mg / cm³. 2 The chloride ion selective barrier material layer has a thickness of 50 micrometers, a total nickel-iron content of 80 wt%, a chloride ion content of 4.0 wt%, and a nickel-iron molar ratio of 5:1. It has a layered structure with an average lateral dimension of 650 nm, an average longitudinal dimension of 22 nm, and a specific surface area of ​​140 m². 2 / g, pore volume 0.42cm 3 / g, with an average pore size of 5.2nm and an interlayer spacing d(003) of 0.8nm.

[0187] The method for manufacturing the chloride ion intercalated nickel-cobalt based hydrotalcite@nitrogen-modified carbon core-shell catalyst is as follows: 820g of nickel nitrate, 139g of cobalt nitrate, 2.1g of urea and 403g of sodium chloride are placed in a 70L reactor and stirred evenly. The mixture is reacted at 180℃ for 6h. After washing and drying, chloride ion modified nickel-cobalt hydrotalcite is obtained. The hydrotalcite is placed in 28g of resorcinol, 14L of formaldehyde, 11L of ethylenediamine and 3L of ethanol aqueous solution (the volume ratio of water to ethanol is 7:3) and stirred at 25℃ for 24h. Then, it is calcined at 700℃ for 10h under an ammonia atmosphere to obtain the chloride ion intercalated hydrotalcite@nitrogen-modified carbon core-shell catalyst.

[0188] (4) An anode slurry was prepared by mixing 5.3 g of cobalt-manganese-based anode catalyst (specifically cobalt-manganese phosphide, with a cobalt-manganese atomic ratio of 3:1 and a phosphorus content of 5.5 wt%), 83 g of 5% Nafion solution, and 59 g of isopropanol. The anode slurry was coated onto the other side of the exchange membrane a material and subjected to hot pressing. The hot pressing conditions included a temperature of 120°C, a pressure of 6 MPa, and a time of 20 min to form an anode with a thickness of 100 micrometers. The loading of the anode catalyst in the anode was 8.5 mg / cm³. 2 Finally, an electrolysis chamber is obtained, the structure of which is shown in Figure 1. From left to right, it includes an anode, an exchange membrane, a cathode, and a chloride ion selective barrier material layer.

[0189] (5) Pass the electrolysis device obtained in (4) into seawater. Using seawater as the water source, prepare a 20wt% sodium hydroxide seawater solution as the electrolyte, whose chloride ions (Cl) 1- The content of [missing information] was 1.7 wt%, the current efficiency Y was 99.7%, Y′ was 99.6%, and after 200 h of reaction, the Cl in the electrolyte was 43000 mg / L. At this point, C0 / C1 was 1.26, Y′ / Y was 0.999, C0' / C1′ was 0.50, and Y1′ / Y1 was 0.998. Electrolysis was started under these conditions: operating temperature 70℃, operating pressure 1.6 MPaG, and operating chamber voltage 2.0 V. The performance evaluation results are shown in Table 1.

[0190] The preparation, assembly, and electrolysis methods of the electrolysis device are the same as in Example 1, except that Q0 / Q1 is 0.985 and I0 / I1 is 0.985.

[0191] Comparative Example 1

[0192] The preparation, assembly, and electrolysis methods of the electrolysis device are the same as in Example 1, except that seawater is used as the water source, and a 2wt% sodium hydroxide seawater solution is prepared as the electrolyte, at which point the CO / C1 ratio is 1.05.

[0193] Comparative Example 2

[0194] (1) 1.9 g of nickel-aluminum alloy cathode catalyst (nickel-aluminum atomic ratio of 5:1) and 26 g of 5% Nafion solution were added to 1.5 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) and ultrasonically mixed to prepare a cathode slurry. This slurry was then coated onto one side of a 25*25 cm anion exchange membrane and subjected to hot-pressing. The hot-pressing conditions included a temperature of 150℃, a pressure of 5 MPa, and a time of 15 min to form a cathode on one side of the exchange membrane. The cathode catalyst loading in the cathode was 3 mg / cm³. 2 The cathode thickness is 40 micrometers.

[0195] (2) The anion exchange membrane is of model Versogen A80, and its functional group is a dimethylpiperidine ion functional group. The thickness of the exchange membrane is 80 micrometers.

[0196] (3) 3.1 mg of chloride-intercalated nickel-iron-based hydrotalcite and 34 g of 5% Nafion solution were added to 88 g of isopropanol aqueous solution (obtained by mixing isopropanol and water at a volume ratio of 3:1) to prepare a chloride-selective barrier material slurry. This slurry was coated onto the cathode and hot-pressed at 200℃ and 15 MPa for 1 min to form a chloride-selective barrier material layer on the cathode surface. The chloride-selective barrier material loading in the chloride-selective barrier material layer was 5 mg / cm³. 2 The chloride ion selective barrier material layer has a thickness of 50 micrometers, a total nickel-iron content of 80 wt%, a chloride ion content of 4.0 wt%, and a nickel-iron molar ratio of 5:1. It has a layered structure with an average lateral dimension of 650 nm, an average longitudinal dimension of 22 nm, and a specific surface area of ​​140 m². 2 / g, pore volume 0.42cm 3 / g, with an average pore size of 5.2nm and an interlayer spacing d(003) of 0.8nm.

[0197] The method for manufacturing the chloride ion intercalated nickel-iron-based hydrotalcite@nitrogen-modified carbon core-shell catalyst is as follows: 556g of nickel nitrate, 125g of ferric nitrate, 1.7kg of urea and 375g of sodium chloride are placed in a 70L reactor and stirred evenly. The mixture is reacted at 150℃ for 6h. After washing and drying, chloride ion-modified nickel-iron hydrotalcite is obtained. This hydrotalcite is then placed in 28g of resorcinol, 14L of formaldehyde, 10.5L of ethylenediamine and 2.8L of an aqueous ethanol solution (water to ethanol volume ratio of 7:3) and stirred at 25℃ for 24h. Finally, it is calcined at 400℃ for 10h under an ammonia atmosphere to obtain the chloride ion intercalated hydrotalcite@nitrogen-modified carbon core-shell catalyst.

[0198] (4) An anode slurry was prepared by mixing 1.9 g of cobalt-manganese based anode catalyst (specifically cobalt-manganese phosphide, with a cobalt-manganese atomic ratio of 3:1 and a phosphorus content of 5.5 wt%), 83 g of 5% Nafion solution, and 59 g of isopropanol. The anode slurry was coated onto the other side of the exchange membrane material and subjected to hot pressing. The hot pressing conditions included a temperature of 120°C, a pressure of 6 MPa, and a time of 20 min to form an anode with a thickness of 37 micrometers. The loading of the anode catalyst in the anode was 3 mg / cm³. 2 Finally, an electrolysis chamber is obtained, the structure of which is shown in Figure 1. From left to right, it includes an anode, an exchange membrane, a cathode, and a chloride ion selective barrier material layer.

[0199] (5) Pass the electrolysis device obtained in (4) into seawater. Using seawater as the water source, prepare a 20wt% sodium hydroxide seawater solution as the electrolyte, whose chloride ions (Cl) 1- The content of [missing information] was 1.7 wt%, the current efficiency Y was 99.7%, Y′ was 99.6%, and after 200 h of reaction, the Cl concentration in the electrolyte was 22000 mg / L. At this point, the ratio of Co / C1 was 1.26, Y′ / Y was 0.999, Co' / C1′ was 0.98, and Y1′ / Y1 was 0.998. Electrolysis was started under these conditions: operating temperature 70℃, operating pressure 1.6 MPaG, and operating chamber voltage 2.0 V. The performance evaluation results are shown in Table 1.

[0200] The preparation, assembly, and electrolysis methods of the electrolysis device are the same as in Example 1, and C0' / C1' is 0.98.

[0201] Comparative Example 3

[0202] The preparation, assembly, and electrolysis methods of the electrolysis device are the same as in Example 1, except that a chloride ion selective barrier material is not used.

[0203] Test method: The membrane electrode was assembled in the electrolytic cell in the following order: end plate, sealing ring, cathode plate, membrane electrode, anode plate, sealing ring, and end plate. The electrolyte was 25% by weight alkaline seawater, with alkalinity derived from sodium hydroxide. A constant voltage test was conducted, and the changes in current and hydrogen production were observed. The hypochlorite ion content in the liquid was recorded in real time. Impurity ions in the solution were analyzed using a UV-Vis spectrophotometer with a sampling interval of 4 hours and a full wavelength scanning method. The chamber voltage was tested using the self-assembled electrolytic cell described above, and the measured chamber voltage was 2V.

[0204] Table 1

Claims

An electrolysis method for chloride-containing water includes the following steps: Chloride-containing water is contacted with a chloride-selective barrier material to obtain treated water. This treated water is then contacted with electrodes to induce a water decomposition reaction, producing oxygen and hydrogen, while simultaneously yielding undecomposed water. The chloride ion selective blocking material is selected to satisfy at least one of the following conditions: 1) the ratio C0 / C1 of the content of chloride ions (Cl 1- ) of said water containing chloride ions (expressed as C0, in wt%) to the content of chloride ions (Cl 1- ) of said non-decomposed water (expressed as C1, in wt%) is comprised between 1.0 and 1.5 (preferably between 1.1 and 1.4), 2) the content of chloride ion (Cl 1- ) in the chloride ion-containing water is 0-7.0 wt% (preferably 0-3.0 wt%) based on the total weight of the chloride ion-containing water being 100 wt%, provided that the content of chloride ion (Cl 1- ) in the chloride ion-containing water is 0 wt%, the current efficiency of hydrogen generation when the decomposition reaction is carried out at a current density of 2000 A / m 2 is Y, provided that the content of chloride ion (Cl 1- ) in the chloride ion-containing water is 7.0 wt%, the current efficiency of hydrogen generation when the decomposition reaction is carried out at the same current density is Y', then Y' / Y is 0.99-1.0 (preferably 0.995-1.0). The electrolysis method of claim 1, wherein the chloride ion selective barrier material is selected to satisfy at least one of the following conditions: 1) Let the time at which the decomposition reaction begins to occur be t0 (in hours), then after t0 + 200 (i.e. 200 hours after the beginning), the ratio C0' / C1' of the value of the content of chloride ions (Cl 1- ) of the water containing chloride ions (assumed to be C0', in wt%) to the content of chloride ions (Cl 1- ) of the undecomposed water (assumed to be C1', in wt%) is 0.15-0.9 (preferably 0.2-0.6), 2) the content of chloride ion (Cl 1- ) in the chloride ion-containing water is 0.2 to 7.0 wt% (preferably 0.2 to 5.0 wt%) based on the total weight of the chloride ion-containing water being 100 wt%, provided that the content of chloride ion (Cl 1- ) in the chloride ion-containing water is 0.2 wt%, the current efficiency of hydrogen gas production when the decomposition reaction is carried out at a current density of 2000 A / m 2 is Y1, provided that the content of chloride ion (Cl 1- ) in the chloride ion-containing water is 5.0 wt%, the current efficiency of hydrogen gas production when the decomposition reaction is carried out at the same current density is Y1', then Y1' / Y1 is 0.992 to 1.0 (preferably 0.996 to 1.0). In the electrolysis method of claim 1, wherein the treated water is brought into contact with the cathode and the anode sequentially, the chloride-containing water is located outside the cathode (and also outside the chloride ion selective blocking material), and is called the cathode-outer electrolyte; the undecomposed water is located outside the anode, and is called the anode-outer electrolyte. The electrolysis method of claim 1, wherein the chloride-containing water (referred to as first chloride-containing water) is provided from the side of the electrode adjacent to the chloride ion selective barrier material, and the chloride-containing water (referred to as second chloride-containing water) is provided from the opposite side of the electrode, wherein the second chloride-containing water mixes with the undecomposed water to form mixed water (the mixed water and the undecomposed water are not distinguished and are collectively referred to as undecomposed water). The electrolytic process as claimed in claim 1, wherein the content of chloride ions (Cl 1- ) is 0-7.0 wt% (preferably 0-3.0 wt%) based on 100 wt% of the total weight of the water containing chloride ions, the remainder being water and unavoidable impurities. The electrolysis method according to claim 1, wherein the content of chloride ions (CI 1- ) is 0-7.0 wt% (preferably 0-3.0 wt%) based on 100 wt% of the total weight of the undecomposed water, with the balance being water and unavoidable impurities. The electrolysis method according to claim 1, wherein the chloride ion selective barrier material is a porous material, wherein Q0 / Q1 is 0.98-1.0 (preferably 0.99-1.0) and I0 / I1 is 0.98-1.0 (preferably 0.99-1.0). The electrolysis process of claim 1, wherein the operating conditions of the decomposition reaction include: Operating temperature: 20-90℃, operating pressure: 0-2.5MPaG, operating voltage: 1.7-2.2V. The electrolysis method of claim 1, wherein the electrodes sequentially comprise a cathode, an anion exchange membrane, and an anode, and the chloride ion selective blocking material is disposed in layers at least at one location: outside the cathode, between the cathode and the anion exchange membrane, and between the anode and the anion exchange membrane. The electrolysis method of claim 9, wherein the cathode, the anion exchange membrane, the anode and the chloride ion selective barrier material layer are independently layered and stacked on top of each other in a zero-gap manner to form a whole. A layered electrode includes an electrode and a chloride ion selective blocking material layer, wherein Q0 / Q1 is 0.98-1.0 (preferably 0.99-1.0) and I0 / I1 is 0.98-1.0 (preferably 0.99-1.0). The layered electrode of claim 11, wherein the electrode sequentially comprises a cathode, an anion exchange membrane, and an anode, and the chloride ion selective blocking material layer is disposed at least at one location: outside the cathode, between the cathode and the anion exchange membrane, and between the anode and the anion exchange membrane. The layered electrode of claim 12, wherein the thickness of the cathode is 80-1000 micrometers, the thickness of the anion exchange membrane is 80-1000 micrometers, the thickness of the anode is 1-800 micrometers, and the thickness of the chloride ion selective blocking material layer is 1-800 micrometers (preferably 20-500 micrometers). The layered electrode of claim 12, wherein the loading amount of the cathode catalyst in the cathode is 0.5-8.0 mg / cm 2 (optimally 4.5-7.5 mg / cm 2 ), the loading amount of the anode catalyst in the anode is 1.0-10.0 mg / cm 2 (optimally 4.5-9.0 mg / cm 2 ), and the loading amount of the chloride ion-selective barrier material in the chloride ion-selective barrier material layer is 0.5-8.0 mg / cm 2 (optimally 3.0-6.0 mg / cm 2 ). The layered electrode of claim 12, wherein the anode catalyst of the anode comprises at least one selected from the elements, alloys, nitrides, phosphides, oxides and hydroxides of nickel, iron, cobalt and manganese; the cathode catalyst of the cathode comprises at least one selected from the elements, alloys, nitrides, phosphides, oxides and hydroxides of nickel, iron, cobalt, manganese, molybdenum and aluminum; the functional groups of the anion exchange membrane are selected from at least one selected from primary amines, secondary amines, tertiary amines, quaternary amines and aromatic amines; the chloride ion selective blocking material is selected from at least one selected from anion intercalation materials, sulfides, phosphides and nitrides, particularly anion intercalated layered metal hydroxides, anion intercalated layered bimetallic hydroxides (LDHs) or chloride ion intercalated LDHs, preferably chloride ion intercalated hydrotalcite materials, and particularly preferably chloride ion intercalated nickel-iron-based hydrotalcites. The layered electrode of claim 15, wherein the anion intercalation material comprises at least two metal elements selected from nickel, iron, cobalt, manganese, aluminum, copper, zinc, chromium, zirconium, and magnesium, preferably at least two metal elements selected from nickel, iron, cobalt, and manganese, and / or, based on 100 wt% of the total weight of the anion intercalation material, the total content of the metal elements is 55-90 wt% (preferably 65-85 wt%), the content of the anions is 2-5 wt% (preferably 3.5-4.8 wt%), and / or, when at least two of the metal elements are included, the molar ratio between the different metal elements is 1:1-10:1 (preferably 1:1-6:1). The layered electrode of claim 15, wherein the anion intercalation material is a sheet structure having an average lateral dimension of 500-2000 nm (preferably 600-800 nm), an average longitudinal dimension of 1-100 nm (preferably 20-60 nm), a specific surface area of 120-300 m 2 / g, a pore volume of 0.35-0.55 cm 3 / g, an average pore diameter of 2-30 nm, and an interlayer spacing d(003) of 0.75-0.9 nm. The layered electrode of claim 12, wherein the cathode, the anion exchange membrane, the anode and the chloride ion selective barrier material layer are independently layered and stacked on top of each other in a zero-gap manner to form a whole. An electrolysis apparatus for chloride-containing water includes an electrolytic cell for containing the chloride-containing water and a layered electrode as described in any one of claims 11-18. A method for manufacturing a layered electrode includes the following steps: A cathode slurry containing a cathode catalyst is coated onto one side of an anion exchange membrane, followed by a first hot-pressing treatment to form a cathode on one side of the anion exchange membrane. An anode slurry containing an anode catalyst is coated onto the other side of the anion exchange membrane, followed by a second hot-pressing treatment to form an anode on the other side of the anion exchange membrane. A slurry containing a chloride ion selective blocking material is applied to at least one location: the outer side of the cathode, between the cathode and the anion exchange membrane, and between the anode and the anion exchange membrane. Then, a third hot-pressing treatment is performed. A method for manufacturing a layered electrode includes the following steps: A pre-formed cathode is positioned on one side of the anion exchange membrane by pressure, a pre-formed anode is positioned on the other side of the anion exchange membrane by pressure, and a pre-formed chloride ion selective barrier material layer is positioned at least at one location: outside the cathode, between the cathode and the anion exchange membrane, and between the anode and the anion exchange membrane by pressure.

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