Ozone water generator

Abstract

To provide an ozone water making apparatus enhanced in electrolytic efficiency on an anode side and enhanced in the making efficiency of ozone water.SOLUTION: The ozone water generator is provided with a cathode 104, a cation exchange membrane 106 permeating cations, an anode 108, and a porous cation exchange membrane layer 107 arranged between the cation exchange membrane 106 and the anode 108 and having a water passage 112 of a porous structure. The anode 108 is: The anode 108 has a plurality of slits.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an ozone water generating apparatus. [Background technology]

[0002] Conventionally, in an apparatus for producing ozone water from raw water by electrolysis, there is a technology in which a cathode having ion exchange performance is provided to suppress a decrease in the efficiency of producing ozone water due to the precipitation of mineral components (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6864939 Summary of the Invention [Problem to be solved by the invention]

[0004] However, in recent years, there has been a demand for solving problems such as improving the electrolysis efficiency not only on the cathode side but also on the anode side to increase the efficiency of ozone water production, but conventional technologies, including the technology of Patent Document 1, are unable to adequately meet such demands.

[0005] The present invention has been made in view of the above circumstances, and has an object to provide an ozone water generation apparatus that improves the electrolysis efficiency on the anode side and has high efficiency in generating ozone water. [Means for solving the problem]

[0006] The ozone water generating apparatus of the present invention is an ozone water generating apparatus that uses electrolysis and includes a cathode, a cation exchange membrane that allows cations to pass through, an anode, and a porous cation exchange membrane layer that is disposed between the cation exchange membrane and the anode and has a porous water passage. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide an ozone water generation apparatus that improves the electrolysis efficiency on the anode side and has high efficiency in generating ozone water. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is an exploded view of an electrolysis cell constituting an ozone water production apparatus according to an embodiment of the present invention. FIG. [Figure 2] FIG. 1 illustrates the mechanism of electrolysis taking place in an electrolysis cell. [Figure 3] FIG. 1 is a diagram showing the molecular structure of a perfluorosulfonic acid polymer that constitutes a cation exchange membrane. [Figure 4] FIG. 1 is a diagram showing the cation permselective function of a cation exchange membrane. [Figure 5] FIG. 1 is a diagram showing the entire electrolysis system of a polymer electrolyte membrane (PEM) water electrolysis method. [Figure 6] 1 is a graph showing the change in ozone concentration over time. [Figure 7] 1 is a graph showing the correlation between water temperature and ozone concentration. [Figure 8] FIG. 1 is a diagram showing the structure of a high-concentration, low-flow-rate electrolytic cell. [Figure 9] FIG. 1 is a diagram showing the structure of a low-concentration, high-flow rate electrolytic cell. [Figure 10] FIG. 1 is a perspective view of a large electrolytic cell in which eight anodes 108 are arranged in a ring. [Figure 11] FIG. 1 is a perspective view of a large electrolysis cell having a double annular water passage. [Figure 12] FIG. 2 is a diagram showing a master for manufacturing an anode. [Figure 13] FIG. 1 is a top view of a single anode. [Figure 14] FIG. [Figure 15] FIG. 1 is a cross-sectional view of a slit structure of an anode. [Figure 16] FIG. 3 is a cross-sectional view showing ozone permeation in an anode 108 according to an embodiment of the present invention. [Figure 17] FIG. 10 is a cross-sectional view showing ozone permeation in a single-plate structure anode of a comparative example. [Figure 18] This is a photograph of the actual master plate used to manufacture the anode. [Figure 19] FIG. [Figure 20] FIG. 10 is a cross-sectional view showing a plate wiring of a comparative example. [Figure 21] FIG. 1 is a cross-sectional view showing a wiring made of titanium fiber according to an embodiment of the present invention. [Figure 22] This is a photograph showing multiple anodes arranged on a titanium fiber. [Figure 23] FIG. 2 is a diagram showing a component configuration according to an embodiment of the present invention. [Figure 24] FIG. 10 is a diagram illustrating a configuration of a comparative example. [Figure 25] FIG. 1 shows structural changes in Nafion carbon in the early stage of ozone generation. [Figure 26] FIG. 10 shows the formation of a cavity after removing the carbon fiber. [Figure 27] FIG. 1 shows the function of the ozone generation stage. [Figure 28] FIG. 10 is a diagram showing the advantages of a Nafion carbon layer. [Figure 29] FIG. 2 is a diagram showing the relationship between a cathode, a Nafion membrane, and an anode. [Figure 30] FIG. 1 shows the formation of three interfaces when Nafion carbon is used. [Figure 31] FIG. 10 is a diagram showing the formation of three interfaces in a comparative example. [Figure 32] FIG. 10 is a diagram showing the effect of improving water flow efficiency in an embodiment of the present invention. [Figure 33] FIG. 10 is a diagram illustrating a problem of high temperature in a comparative example. [Figure 34] FIG. 2 is a diagram showing a cupra element body. [Figure 35] FIG. 1 is a diagram showing the state in which cupra is coated with Nafion. [Figure 36] FIG. 10 is a diagram showing the water flow state of cupra. [Figure 37] 10 is a photographic image showing the state of Nafion felt with a cupra substrate before and after electrolysis. [Figure 38] This is a performance comparison table between cupra products and existing products. [Figure 39] This is a table showing the change in ozone concentration over time for cupra products and existing products. [Figure 40] 1 is a performance comparison table of glass fiber substrates. [Figure 41] 1 is a performance comparison table of polytetrafluoroethylene substrates. [Figure 42] FIG. 1 is a diagram showing the bubble adhesion phenomenon in a polytetrafluoroethylene substrate. [Figure 43] FIG. 1 is a diagram showing the structure of a polytetrafluoroethylene and cupra composite substrate. [Figure 44] 1 is a table showing the performance of a polytetrafluoroethylene + cupra substrate. [Figure 45] FIG. 1 is a diagram showing the relationship between current and voltage in electrolysis. [Figure 46] FIG. 1 is a graph showing the correlation between the current value and the ozone concentration, voltage, and amount of hydrogen produced during electrolysis. [Figure 47] FIG. 1 is a diagram showing the permeation of hardness components (metal cations) through an ion exchange membrane. [Figure 48] FIG. 1 illustrates passivation by deposition of metal cations at the cathode. [Figure 49] FIG. 1 illustrates continuous positive ion ejection according to the present invention. [Figure 50] FIG. 2 is a diagram showing the relationship between an ion exchange membrane, a solid acid catalyst cathode, and a cathode. [Figure 51] FIG. 1 is a diagram showing the structure of a solid acid catalyst cathode. [Figure 52] FIG. 10 is a diagram showing the electrolysis action in a PEM system of a comparative example. [Figure 53] FIG. 1 is a diagram showing the electrolysis action of a PEM system using a solid acid catalyst in the present embodiment as a cathode. [Figure 54] FIG. 1 is a diagram showing a hypothetical situation in which calcium hydroxide is produced in the environment of the solid acid catalyst of the present embodiment. [Figure 55] FIG. 10 is a diagram showing a hypothetical situation in which calcium hydroxide is produced in a comparative example. [Figure 56]FIG. 1 shows the overall assembled electrolysis cell. [Figure 57] FIG. [Figure 58] FIG. 1 is a diagram showing the state of the ion exchange membrane surface when a solid acid catalyst cathode is not used. [Figure 59] FIG. 1 is a diagram showing the state of the ion exchange membrane surface when a solid acid catalyst cathode is used. [Figure 60] These are actual images showing the state of the electrolytic surface (left) and intermediate layer (right) of a solid acid catalyst cathode. [Figure 61] 1 is a photographic image showing the state of the cathode surface. [Figure 62] 1 is a photographic image showing deposits accumulated on the cathode. [Figure 63] 10 is a photographic image showing the deposit discharged from the discharge port. [Figure 64] FIG. 1 is a diagram showing a conventional strong acid cleaning system as a comparative example. [Figure 65] FIG. 1 is a diagram showing an in-line use configuration of an electrolysis cell 1 according to an embodiment of the present invention. [Figure 66] FIG. 1 illustrates a remixing system in a hydrogen discharge constrained environment. [Figure 67] FIG. 1 is a diagram showing an electrolytic cell for immersion use according to a comparative example. [Figure 68] FIG. 10 is a diagram showing the state of hydrogen and mineral release during immersion use in a comparative example. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

[0010] Fig. 1 is an exploded view of an electrolysis cell constituting an ozone water production apparatus according to an embodiment of the present invention, and Fig. 2 is a diagram showing the mechanism of electrolysis performed in the electrolysis cell.

[0011] The ozone water generator according to an embodiment of the present invention is an apparatus for efficiently producing highly concentrated ozone water from raw water by electrolysis. While conventional electrolysis cells have insufficient electrolysis efficiency on the anode side, the ozone water generator according to an embodiment of the present invention has a porous cation exchange membrane layer having porous water passages between the cation exchange membrane and the anode, thereby forming a large number of three interfaces on the electrolysis surface, significantly improving the electrolysis efficiency and enabling the production of ozone water to be increased.

[0012] As shown in FIG. 1 , the electrolysis cell 1 according to the embodiment of the present invention includes, in order from the top, a waterproof / current-carrying power supply electrode 101, a holder lid 102, an internal pressure spring 103, a SUS cathode 104, a solid acid catalyst cathode 105, a cation exchange membrane (Nafion membrane) 106, a porous cation exchange membrane layer (Nafion carbon) 107, an anode 108, titanium fiber 109, a holder body 110, and a waterproof / current-carrying power supply electrode 111.

[0013] The function of each component will be explained below. The waterproof / current-carrying power supply electrodes 101, 111 apply power to the electrolysis cell 1 from the outside and provide pressure resistance and waterproofing. The holder lid 102 is the top cover of the electrolysis cell and is equipped with an outlet 102a for the hydrogen / mineral water W. The internal pressure spring 103 is designed to hold the SUS cathode 104 to the anode 108 in close contact, and is, for example, 10 kgf / cm 2The SUS cathode 104 is a stainless steel cathode with a punch structure 104a (described later) for uniformly distributing electricity and pressure to the solid acid catalyst cathode 105 and discharging the generated hydrogen gas and mineral water W. The solid acid catalyst cathode 105 functions to transport minerals in the water W to the cathode for deposition and discharge. The cation exchange membrane 106 is a solid polymer membrane with cation exchange and conductivity functions, and functions to separate ozone O3 from hydrogen gas. The porous cation exchange membrane layer 107 has a porous water passage 112 and functions to improve electrolysis efficiency. The anode 108 is, for example, a boron-doped diamond (BDD) catalyst, and generates ozone O3 through electrolysis. The titanium fiber 109 supplies electricity to the anode 108, allowing water W to flow between the fibers while efficiently channeling the generated ozone O3 into the water passage 112. The holder body 110 is a housing for the electrolysis cell and has a water inlet and outlet.

[0014] The principle of electrolysis will be explained with reference to Figure 2. The anode 108 removes electrons e from the material in contact with it. Water W loses its structure due to the electrons e, and oxygen becomes O2 or ozone O3 due to the action of the catalyst. Meanwhile, hydrogen ions H (H+) and cations such as calcium ions (Ca2+) contained in raw water such as tap water and groundwater are attracted to the SUS cathode 104 and permeate the cation exchange membrane 106. The SUS cathode 104 provides electrons e to the material in contact with the cathode. The provision of electrons e causes the hydrogen ions H to become hydrogen gas (H2), and the calcium ions to become calcium-based crystals. In this way, ozone O3 is generated on the anode 108 side, and hydrogen gas and a metal ion precipitate P are generated on the cathode 104 side.

[0015] The technical features of the anode 108 configured as a BDD used in the embodiment of the present invention will be described.

[0016] As a comparative example, when a copper anode is used, the anodic reaction during electrolysis involves the loss of electrons e, and the anode material itself is no exception, resulting in the corrosion of the copper anode itself. Specifically, copper ions (Cu2+) are generated when electrons e (e-) are lost from copper (Cu), which then precipitate as copper hydroxide (Cu(OH)2). Because the loss of electrons e and corrosion are essentially synonymous, with a copper anode, some of the energy that should be used to decompose water (W) is consumed by the corrosion of the anode itself, resulting in a problem of reduced ozone (O3) generation efficiency.

[0017] In contrast, when an anode 108 made of BDD according to an embodiment of the present invention is used, the anode 108 made of BDD, which is diamond doped with boron (boron), is conductive because it contains free electrons. Because the anode 108 made of BDD has a structure that does not corrode in the anodic reaction, all of the energy that would corrode a metal anode in the comparative example is used to decompose water W. As a result, hydrogen ions H (H+) and oxygen (O) are generated from water W (H2O), and the oxygen acts as a catalyst to efficiently generate not only O2 but also ozone O3.

[0018] The technological advantage of the anode 108 made of BDD is that it has a wide potential window. This enables stable electrolysis at high potentials that are not possible with metal electrodes, which is the comparative example, and enables the generation of high-concentration ozone O3. In addition, because the anode 108 made of BDD is extremely chemically stable, it can maintain stable ozone O3 generation performance over a long period of time, contributing to an extended lifespan of the electrolysis cell 1. Materials with a potential window similar to BDD can also be used for ozone generation.

[0019] The structure and function of the cation exchange membrane 106 used in the embodiment of the present invention, and the solid polymer water electrolysis method using the same will be described with reference to FIGS. 3, 4 and 5.

[0020] Fig. 3 is a diagram showing the molecular structure of the perfluorosulfonic acid polymer that constitutes the cation exchange membrane 106. Fig. 4 is a diagram showing the cation permselective function of the cation exchange membrane 106. Fig. 5 is a diagram showing the entire electrolysis system of a solid polymer water electrolysis method (Polymer Electrolyte Membrane method, hereinafter referred to as "PEM method").

[0021] As shown in Figure 3, the cation exchange membrane 106 is made of, for example, perfluorosulfonic acid polymer, a rubber-like polymer with sulfonic acid groups (-SO3-H+) in the fluorine-based main chain. This structure is similar to the properties of solid sulfuric acid, but because it is solid, it will not leak and is highly safe. Perfluorosulfonic acid polymer is extremely chemically stable, and can maintain stable performance for long periods of time even in high-temperature, high-pressure electrolysis environments.

[0022] The function of the cation exchange membrane 106 will be described with reference to Figure 4. The cation exchange membrane 106 forms a channel structure with sulfonic acid groups arranged on the inside. This sulfonic acid channel has the function of allowing only cations such as hydrogen ions H (H+) and calcium ions (Ca2+) to pass through in one direction from the anode 108 side. On the other hand, it has the selectivity to block the passage of molecules and anions such as water W and ozone O3. The hydrogen ions H and calcium ions bond with the sulfonic acid groups, and by repeatedly bonding, they reach the cathode 104, where they receive electrons e, are converted into molecules, and are then discharged.

[0023] As shown in Figure 5, the embodiment of the present invention employs a PEM system. In this system, a conductive cation exchange membrane 106 is placed between the anode 108 and cathode 104 of the electrolytic cell, enabling stable electrolysis even with pure water or low-hardness water, which does not readily conduct electricity. Furthermore, this system has the advantages of enabling reliable separation of the products on the anode 108 side and the cathode 104 side, and facilitating assembly of the electrolytic cell. Thus, solid polymer water electrolysis is a suitable method for the ozone water generating electrolytic cell 1.

[0024] 6 and 7, the physicochemical properties and dissolution mechanism of ozone O3 generated in the embodiment of the present invention, and the correlation between concentration, flow rate, and power in the electrolysis cell 1 will be described.

[0025] The effects of ozone O3 have been confirmed in a wide range of areas, including sterilization, deodorization, bleaching, and immune enhancement, all of which are due to its powerful oxidative reaction. Ozone O3 is an unstable molecule containing three oxygen atoms that reacts with target substances to exert its oxidative effect. Ozone O3 molecules act as oxygen radicals on bacteria B, destroying their cell walls and membranes through oxidation, thereby exerting its sterilizing effect. Ozone O3 is said to have an oxidizing power approximately seven times that of chlorine, and its powerful oxidative reaction destroys and inactivates the cell membranes and protein structures of bacteria and viruses. It also causes oxidative decomposition of organic substances, resulting in deodorizing and bleaching effects. Furthermore, trace amounts of ozone O3 are believed to stimulate the immune system by causing moderate oxidative stress in the body, contributing to immune enhancement.

[0026] The decrease in ozone O3 concentration over a few minutes, or its deactivation over time, is thought to be due to ozone O3 molecules reacting with each other and bonding with oxygen. Ozone O3 molecules undergo the decomposition reaction 2O3 → 3O2, resulting in the decomposition of ozone O3 into oxygen. This decomposition reaction occurs naturally, and the half-life of dissolved ozone O3, especially in water, is thought to be on the order of a few minutes to a few tens of minutes. The oxygen radicals generated during this decomposition process have strong oxidizing power, resulting in sterilization and organic matter decomposition. Environmental factors such as temperature, pH, and impurities in the water affect the decomposition rate, with decomposition being accelerated under high temperature or high pH conditions. The presence of metal ions and organic matter can also catalytically promote decomposition.

[0027] Next, we will explain the deactivation over time at high concentrations of ozone O3. At high concentrations of ozone O3, the distance between ozone O3 molecules is short, so reactions between ozone O3 molecules occur frequently, resulting in rapid deactivation. When many ozone O3 molecules are densely packed together, the ozone O3 molecules react violently with each other and are rapidly decomposed into oxygen. In a high-concentration ozone O3 environment, the average distance between each ozone O3 molecule decreases, increasing the frequency of collisions between molecules and the probability of reaction. This phenomenon is called the "ozone autolysis reaction," and it becomes more pronounced as the ozone O3 concentration increases. Furthermore, a "chain reaction" occurs in which hydroxyl radicals and reactive oxygen species generated by the decomposition of ozone O3 decompose other ozone O3 molecules in a chain reaction, accelerating the decomposition rate nonlinearly.

[0028] Furthermore, we explain the deactivation over time at low concentrations of ozone O3. At low concentrations, ozone O3 molecules are far apart, so the frequency of reactions between ozone O3 molecules is low and deactivation takes time. In low-concentration environments, the average distance between ozone O3 molecules increases, reducing the frequency of intermolecular collisions. This suppresses the self-decomposition reaction of ozone O3, resulting in a relatively long half-life. Furthermore, the large intermolecular distance reduces the continuity of the chain reaction, increasing the probability of reaction termination and slowing the overall decomposition rate. From a practical perspective, this suggests that when long-term sterilization or disinfection effects are required, sustained application of low concentrations is more effective than high concentrations.

[0029] Referring to Figure 6, the change in ozone O3 concentration over time will be explained. The horizontal axis of the graph represents time, and the vertical axis represents ozone O3 concentration. When the ozone O3 concentration is high, the rate of decrease is rapid and the slope is steep. In contrast, as the ozone O3 concentration decreases over time, the slope of the decrease in ozone O3 concentration becomes smaller. In other words, when the ozone O3 concentration is high, the reactivity is high, and when the ozone O3 concentration is low, the reactivity is low. As is clear from this graph, the decomposition rate of ozone O3 is concentration-dependent and exhibits an exponential decay pattern. A rapid decrease in concentration occurs in the initial stage, and the decay rate becomes slower over time. This is because the probability of intermolecular reactions is directly proportional to the concentration. These characteristics are important for understanding the relationship between the timing of ozone water use and the duration of its effectiveness, and they also significantly affect the design and operation of ozone water generation devices. In particular, they demonstrate the usefulness of the ozone water generation device according to an embodiment of the present invention, which is intended for immediate use.

[0030] In ozone O3 generation, flow rate and concentration tend to be roughly inversely proportional. When operating the same electrolytic cell with the same power, increasing the flow rate tends to decrease the concentration, while decreasing the flow rate tends to increase the concentration. The electrolytic cell 1 according to an embodiment of the present invention can generate high-concentration ozone water of 20 mg / L at a low flow rate of 100 ml / min. However, increasing the flow rate decreases the concentration, reaching 2 mg / L at 1000 ml / min and 1 mg / L at 2000 ml / min. This relationship arises from the fact that the total amount of ozone O3 generated by electrolysis remains constant. At low flow rates, the same amount of ozone O3 dissolves in a smaller amount of water, resulting in a higher concentration. At high flow rates, the same amount of ozone O3 dissolves in a larger amount of water, resulting in a lower concentration. Understanding this characteristic allows optimal operating conditions to be set for each application. For example, a high-concentration, low-flow rate setting is suitable for cleaning medical equipment that requires high sterilization power, while a low-concentration, high-flow rate setting is suitable for cleaning large-area surfaces.

[0031] There is also a correlation between power, lifespan, and ozone O3 output. Increasing power increases ozone O3 output and ozone O3 concentration, but the higher ozone O3 concentration leads to a steeper decline in ozone O3 concentration. Conversely, decreasing power decreases ozone O3 output and ozone O3 concentration, but the lower ozone O3 concentration leads to a steeper decline in ozone O3 concentration. At a high power of 20 W, high ozone generation capacity is achieved, but device lifespan is limited to approximately 100 hours. In contrast, at a low power of 5 W, generation capacity decreases, but lifespan extends to approximately 2000 hours. At an intermediate power of 10 W, a lifespan of approximately 500 hours can be expected. The main factors behind this relationship are heat generation and electrode material degradation due to high-power operation. High-power operation significantly increases the temperature of the electrode surface, accelerating the degradation of the anode 108. Furthermore, the strong electric field generated by high power also places strain on the ion-exchange membrane, accelerating its degradation. In practice, it is important to select the optimal power setting by considering the balance between the required ozone concentration and the lifespan of the device. If long-term continuous use is expected, operation at low to medium power settings is recommended.

[0032] The correlation between water temperature and ozone O3 concentration is explained with reference to Figure 7. It is generally known that the higher the water temperature, the smaller the dissolved amount of ozone O3. As shown in the graph, the ozone O3 concentration tends to decay more rapidly in the following order: 10°C, 20°C, and 30°C. Figure 7 clearly shows the change in ozone concentration over time under different water temperatures, starting from the same initial concentration (20 mg / L). At the low temperature of 10°C, the ozone concentration remains at approximately 9 mg / L even after 15 minutes, whereas at the high temperature of 30°C, it drops to approximately 1 mg / L after the same 15 minutes. At the medium temperature of 20°C, the ozone concentration shows an intermediate decay trend, reaching approximately 5 mg / L after 15 minutes. This temperature dependency is an important consideration for the practical use of ozonated water. Operational design must take into account the rapid decrease in ozone concentration, especially in summer and for hot water applications. The ozone water generating device according to the embodiment of the present invention has the advantage of being able to minimize the influence of temperature due to its characteristic of being able to generate ozone water immediately before use.

[0033] The aforementioned trend is attributed to the fact that higher temperatures accelerate the deactivation of ozone O3 over time, resulting in the ozone O3 being squeezed out by moving water molecules. At high water temperatures, i.e., when molecular motion is intense, water molecules move in and out of the gaps between water molecules containing ozone O3, expelling the ozone O3 and vaporizing it. The active movement of water molecules associated with rising temperature pushes out ozone O3 molecules that had been dissolved in the gaps between water molecules. At high temperatures, the thermal kinetic energy of water molecules increases, increasing the frequency and energy of intermolecular collisions. This results in a "solubility decrease," in which ozone O3 molecules that had been dissolved in the structural gaps of water molecules are physically pushed out. Furthermore, rising temperatures decrease the Henry's constant, which determines the solubility of gases in water, leading to a preference for ozone O3 partitioning into the gas phase rather than the liquid phase. Furthermore, high temperatures also accelerate the self-decomposition reaction of ozone O3 in water. These combined factors cause a rapid decrease in ozone O3 concentration with increasing water temperature.

[0034] Water molecules are bent in a dogleg shape. This is due to the electrical force inherent in water molecules. A water molecule (H2O) has an asymmetric structure with an oxygen atom (O) at its center, to which two hydrogen atoms (H) are bonded at an angle of approximately 104.5 degrees. This structure arises from the strong electronegativity of the oxygen atom. Because oxygen atoms attract electrons more strongly than hydrogen atoms, an imbalance in the charge within the molecule occurs. As a result, the oxygen side carries a partial negative charge and the hydrogen side carries a partial positive charge, forming a "dipole molecule." This electrical imbalance is the basis for water's unique properties. In particular, the ability of this molecular structure to form hydrogen bonds significantly influences the physical and chemical properties of water and is also involved in the mechanism of ozone (O3) dissolution.

[0035] Water W (liquid) is a state in which countless water molecules with a bent-line structure are stacked one on top of the other, creating gaps between the water molecules. The formation of these gaps is due to the hydrogen bond network between water molecules. Water molecules form hydrogen bonds when the two lone electron pairs of oxygen atoms attract each other to the hydrogen atoms, but due to the constraints of the molecular geometry and bond angle, they cannot form a perfectly packed structure. As a result, tiny gaps form between the molecules. The size and number of these gaps change depending on the temperature and pressure. At low temperatures, the hydrogen bond network becomes more regular and stable, and the gaps are more clearly formed. On the other hand, at high temperatures, the thermal motion of the molecules becomes more active, causing the hydrogen bond network to become disordered and the gap structure to change.

[0036] This section explains the dissolution state of gas molecules in the gaps between water molecules. When a gas, including ozone water, is dissolved in water (W), the gas molecules are considered to have entered the gaps between these water molecules. Because ozone O3 is originally a gaseous component, increasing the surface area of ​​the solvent (water W) tends to disperse it into the air, reducing its concentration. Therefore, shower-like spraying is preferable for ozone water products, even if it is very fine. Spraying is difficult because it is difficult to obtain a sufficient amount of liquid on the target object and ozone O3 disperses during spraying, making it a disadvantageous method of using ozone O3. Ozone O3 molecules, due to their three-dimensional structure (curved V-shape) and size, are arranged in a specific manner in the gaps between water molecules. Weak van der Waals forces act between ozone O3 molecules and surrounding water molecules, temporarily stabilizing them. However, because this interaction is not as strong as hydrogen bonding, it is easily disrupted by changes in environmental conditions (e.g., increased temperature, decreased pressure, or pH fluctuations). Furthermore, an increase in the water surface area increases the gas-liquid interface, facilitating the transition of ozone O3 to the gas phase according to Henry's law. For this reason, in the practical use of ozonated water, a flooding method that minimizes the liquid surface area is recommended.

[0037] The flow rate control structure design of the holder body 110 in the electrolysis cell 1 according to the embodiment of the present invention will be described with reference to FIGS.

[0038] Fig. 8 is a diagram showing the structure of a high-concentration, low-flow rate electrolytic cell. Fig. 9 is a diagram showing the structure of a low-concentration, high-flow rate electrolytic cell. Fig. 10 is a perspective view of a large electrolytic cell in which eight anodes 108 are arranged in a ring. Fig. 11 is a perspective view of a large electrolytic cell having a double ring-shaped water passage 114.

[0039] A high-concentration, low-flow-rate electrolysis cell will be described with reference to Figure 8. This structure does not have a water passage. Instead, the slit structure 108a of the anode 108 shown on the left and the spiral flow path structure 113 shown on the right restrict the flow rate of water W, producing highly concentrated ozone water. Because there is no water passage, water is concentrated and passes through the slit structure, allowing the ozone O3 generated by electrolysis to efficiently dissolve in the water W, resulting in a high concentration. This high-concentration, low-flow-rate electrolysis cell is designed to maximize the contact time between ozone O3 and water by intentionally restricting the water flow path, thereby increasing the dissolved ozone concentration. The slit structure 108a of the anode 108 ensures an adequate electrolysis area for ozone O3 generation while preventing the generated ozone O3 from being quickly washed away by the water flow. The spiral flow path structure 113 on the right creates a vortex in the water flow, reducing the flow rate and promoting the dissolution of ozone O3 into water. This design is ideal for applications such as disinfecting medical equipment and cleaning dental instruments, where small volumes of highly concentrated ozone water are required.

[0040] Referring to Figure 9, we will explain the low-concentration, high-flow electrolysis cell. This structure is equipped with a water channel 112. The left side shows the state with the anode 108 installed, and the right side shows the state without the anode 108. The presence of the water channel 112 increases the flow rate of water W, relatively reducing the ozone O3 concentration, but allowing for the efficient production of large amounts of ozone water. The high-concentration and low-concentration types each have one anode 108 with the same specifications, and while the ozone O3 generation capacity itself is similar, the ozone O3 concentration is determined by the flow rate of water W. In this low-concentration, high-flow type, the explicit water channel 112 reduces water flow resistance within the electrolysis cell, allowing for the treatment of larger volumes of water. The water channel 112 not only functions as a pathway, but also precisely controls the flow rate through its cross-sectional area and shape. The presence of the water channel 112 also optimizes the pressure distribution within the electrolysis cell, providing an environment for efficient electrolysis reactions. This low-concentration, high-flow configuration is suitable for applications requiring large volumes of relatively low-concentration (1-2 mg / L) ozonated water, such as large-area surface cleaning and agricultural water treatment.

[0041] Referring to Figure 10, we will describe a large-scale electrolysis cell with eight anodes 108 arranged in a ring. The ring-shaped arrangement of multiple anodes 108 prevents the heat-generating surfaces from concentrating, resulting in an electrode configuration with high heat dissipation efficiency. Furthermore, shaping a single large anode is prone to distortion during the shaping process, which can lead to loss of flatness when the anode is tightly attached. However, arranging smaller anodes eliminates distortion and ensures flatness. When a large-area anode 108 is required, arranging multiple small anodes 108 with microstructured BDDs allows for the combination of anodes 108 with BDDs of any desired area while maintaining the benefits of the microstructure. Furthermore, maintaining a distance between the anodes 108 with each BDD also improves heat dissipation efficiency. This ring-shaped arrangement offers significant advantages in terms of thermal management. The anodes 108 are spaced apart, preventing the heat generated by each electrode from concentrating, allowing for efficient heat dissipation. Furthermore, the inclusion of a water channel in the center of the ring allows for efficient cooling from the inside as well. Furthermore, this configuration contributes to uniform current distribution, reducing the risk of overheating and electrode damage due to local current concentration. The parallel arrangement of the electrodes increases overall processing capacity while maintaining the current density applied to each electrode within an optimal range. Another advantage is that redundancy is ensured, preventing the entire system from completely shutting down even if one electrode malfunctions.

[0042] Referring to Figure 11, a large-scale electrolytic cell with a double-annular water passage 114 will be described. The double-annular water passage 114 is located below the anode 108, and this water passage 114 structure enables flow rate control. By inserting a packing 115 (not shown) that fills this water passage 114, the same holder body 110 can be used for both high-concentration, low-flow rate electrolytic cells and low-concentration, high-flow rate electrolytic cells. Because the packing 115 is exposed to high-concentration ozone (O3), it is preferable to use a material with excellent ozone resistance, such as polytetrafluoroethylene (PTFE). This double-annular water passage structure not only controls the flow rate but also plays an important role in ensuring uniformity of the water flow. The double-annular design allows for different flow rates and velocities in the inner and outer water passages, optimizing the water flow distribution within the cell. Furthermore, by adjusting the insertion position and number of the packing 115, the opening area of ​​the water passage can be gradually changed, providing flexibility to accommodate various flow rate conditions. This feature allows for a cost-effective system that can be used for a variety of purposes with a single device. The use of ozone-resistant materials is important for ensuring reliability over long-term operation, and PTFE in particular has extremely high resistance to chemical degradation by ozone.

[0043] The configuration of the anode 108 and the wiring system using titanium fibers 109 used in the embodiment of the present invention will be described with reference to FIGS.

[0044] FIG. 12 is a diagram showing a master 116 for the anode 108. FIG. 13 is a top view of a single anode 108. FIG. 14 is a cross-sectional view of the anode 108. FIG. 15 is a cross-sectional view of the slit structure 108a of the anode 108. FIG. 16 is a cross-sectional view showing ozone permeation in the anode 108 according to an embodiment of the present invention. FIG. 17 is a cross-sectional view showing ozone permeation in a single-plate structure anode of a comparative example. FIG. 18 is a photograph of an actual manufacturing master for the anode. FIG. 19 is an enlarged photograph of the anode 108. FIG. 20 is a cross-sectional view showing plate wiring of a comparative example. FIG. 21 is a cross-sectional view showing wiring made of titanium fiber 109 according to an embodiment of the present invention. FIG. 22 is a photograph showing a state in which multiple anodes 108 are arranged on titanium fiber 109.

[0045] The manufacturing process of the anode 108 will be described with reference to FIG. 12 . The anode 108 is produced by cutting a niobium plate 117, which is one embodiment of a master 116, into the shape shown in FIG. 12 and then coating it with BDD. As shown in the figure, multiple anodes 108 are efficiently arranged on a single master 116. Because BDD coating is a particularly expensive process, the above method is used to improve production efficiency and reduce the price per anode 108. Each anode 108 on the master 116 is optimally arranged to maximize manufacturing efficiency. The niobium plate 117 was selected as the substrate for its electrical conductivity and corrosion resistance, and the BDD coating is then applied thereto. The BDD coating manufacturing process is complex and requires advanced technology, and employs techniques such as microwave plasma CVD (chemical vapor deposition) and hot filament CVD under high-temperature and high-pressure environments. In the coating process, a carbon source gas, such as methane, and a boron dopant gas are mixed in a precise ratio to form a uniform film on the niobium plate 117. This process requires strict control, as the boron concentration, film thickness, and crystallinity directly affect electrode performance. Individual anodes 108 are cut out of the completed master using precision cutting technology. This batch manufacturing method ensures uniform quality and reduces costs.

[0046] Referring to Figure 13, the structure of a single anode 108 is described. The anode 108 has an asymmetrical octagonal structure with numerous slit structures 108a inside. The dotted circle in the figure indicates the outer diameter of the anode 108, and the internal linear structure represents the slit pattern. The slit structures 108a enable efficient mixing of the water flow and ozone (O3). This design has the advantage of ensuring uniform current distribution and minimizing current concentration due to edge effects. The internal slit pattern is not simply straight; it has been optimized to balance electrolysis efficiency and mechanical strength. The width and spacing of the slits are designed to achieve both ozone (O3) generation efficiency and structural stability. Furthermore, the slit structures 108a not only increase the electrolysis area but also function as diffusion paths for the generated ozone (O3). This allows ozone (O3) to efficiently dissolve in water without remaining on the electrode surface. This design was optimized based on fluid dynamics simulations and experimental verification, achieving high ozone water generation efficiency.

[0047] The cross-sectional structure of the anode 108 is described with reference to Figure 14. The top plan view and bottom cross-sectional view clearly show the three-dimensional structure of the anode 108. The hatched area at the bottom indicates the niobium plate 117, whose surface is coated with a BDD coating. As is clear from the cross-sectional view, the anode 108 has a relatively thin plate-like structure, which reduces electrical resistance and improves thermal conductivity. The thickness of the niobium plate 117 is optimized to balance mechanical strength and processability. The BDD coating formed on the niobium plate 117 is a thin layer (several micrometers to several tens of micrometers), but its fine crystalline structure exhibits high electrochemical stability and catalytic activity. The BDD coating is uniformly applied not only to the surface but also to the inner wall surfaces of the slits, enabling efficient ozone (O3) generation even in the slit area. The cross-sectional shape and dimensions are also optimized from a hydrodynamic perspective, promoting turbulence in the water flow and enabling efficient mixing and dissolution of the generated ozone (O3).

[0048] Referring to Figure 15, a cross section of the slit structure 108a of the anode 108 is described. The slit structure 108a of the anode 108 has a cation exchange membrane (Nafion membrane) 106 on top and an electrolysis surface 125 below. Ozone (O3) is generated here and efficiently supplied to the water flow below through the slit structure 108a. The cross section of the slit structure 108a is not a simple linear cut but is designed to maximize hydrodynamic effects. The width and depth of the slit are optimized to balance the resistance of the water flow and the diffusion efficiency of the ozone (O3). The inner walls of the slits are also coated with BDD, which significantly increases the effective area for the electrolysis reaction. The main electrolysis reaction occurs on the upper electrolysis surface 125, which is in contact with the cation exchange membrane (Nafion membrane) 106. The generated ozone (O3) moves downward through the slit structure 108a. This slit structure 108a plays an important role in both the generation and transportation of ozone (O3). In addition, the increased surface area created by the slits allows more ozone (O3) to be produced with the same volume of electrode, contributing to the efficiency and compactness of the overall system.

[0049] Referring to Figure 16, the mechanism of ozone O3 permeation through the anode 108 according to an embodiment of the present invention will be described. Water W passing through the gaps in the anode 108 reaches the electrolytic surface 125 of the cation exchange membrane (Nafion membrane) 106. Ozone O3 then permeates the slit structure 108a, efficiently adding ozone O3 to the water flow. The arrows in the figure indicate the flow of ozone O3. The anode design with the slit structure 108a according to an embodiment of the present invention comprehensively optimizes the generation and transfer of ozone O3 into the water. Ozone O3 generated on the electrolytic surface 125 is directly guided into the water flow through the slit structure 108a. This structure minimizes the residence time of ozone O3 on the electrode surface and suppresses loss due to autolysis. Furthermore, the water flow passing through the slits creates moderate turbulence, enhancing the efficiency of ozone O3 dissolution. Another important feature is that the water flow can directly contact the cation exchange membrane (Nafion membrane) 106 and the electrolytic surface 125, thereby constantly supplying the water necessary for the electrolysis reaction. As a result, it is possible to produce ozone water with a higher concentration with the same power input compared to a single-plate anode. This efficient ozone O3 permeation mechanism is a core technical element of the high ozone water production efficiency according to the embodiment of the present invention.

[0050] Referring to FIG. 17, a comparative example of a single-plate anode is described. The comparative example demonstrates that the efficiency of ozone O3 flowing into the water flow is poor due to the anode's single-plate structure. It can be seen that the efficiency of supplying ozone O3 to the water flow is significantly inferior compared to this embodiment, which includes the slit structure 108a according to the present invention. With a single-plate anode, the path for ozone O3 to migrate from the electrode surface into the water is limited. The generated ozone O3 must diffuse along the electrode surface, reducing its contact efficiency with the water flow. This structure increases the residence time of ozone O3 on the electrode surface, increasing losses due to the self-decomposition reaction. Furthermore, insufficient contact between the electrode surface and the water flow limits the supply of fresh water required for the electrolysis reaction. Furthermore, the single-plate structure makes it difficult to suppress temperature increases on the electrode surface, which also accelerates the decomposition of ozone O3. These issues significantly reduce the efficiency of ozone water production with a single-plate anode. Comparing the design of the comparative example with the design according to the present invention demonstrates why the introduction of the slit structure 108a contributes to improved ozone water production efficiency.

[0051] Figure 18 is a photograph of an actual anode manufacturing master. Numerous BDD-coated particles are embedded in the niobium scrap, presumably generated during processing. The penetration of ozone (O3) through these slits may contribute to the increased ozone (O3) concentration. The high-resolution image clearly reveals the fine structure of the slit structure 108a. Inside the slits, there are tiny niobium particles generated during the processing process, which are also BDD-coated. These particles are not simply processing residues; they actually increase the effective surface area for the electrolytic reaction, improving the ozone (O3) generation efficiency. These particles also create micro-turbulence in the water flow, promoting the dissolution of ozone (O3). The slit width is precisely controlled, achieving optimal water flow resistance and ozone (O3) penetration efficiency. This precisely processed microstructure is a key factor supporting the high ozone water generation performance of embodiments of the present invention.

[0052] Referring to Figure 19, we will explain the enlarged image of the anode 108. The actual surface condition of the anode 108 can be observed in detail, confirming the precision of the slit processing and the state of the BDD coating. It is important that the BDD coating is uniformly applied even within the slits. The BDD coating has a polycrystalline structure, and characteristic grain boundaries can be observed on its surface. This crystalline structure functions as an electrochemically active site, enabling efficient ozone (O3) generation. A uniform BDD coating can also be observed in the slit area, indicating that the entire slit functions as an effective electrolytic reaction field. The fine irregularities observed on the surface increase the effective surface area and enhance contact efficiency with water. Furthermore, the niobium plate 117 and the BDD coating exhibit excellent adhesion, contributing to the long-term durability of the electrode. This optimization at the microstructure level supports the high performance and reliability of the ozone water generator according to an embodiment of the present invention.

[0053] There are several technical challenges in the manufacturing process of the anode 108. Because the BDD coating applied during the anode manufacturing process places a large load on the niobium substrate, manufacturing an anode 108 composed of a BDD larger than a certain size can result in distortion (although distortion is negligible for an area of ​​a few square centimeters). To address this distortion, it is recommended that the niobium substrate be 2 mm or thicker. However, when fabricating a microstructure such as the anode 108 used in the embodiment of the present invention, the thickness must be 1 mm or less for cutting purposes, making it difficult to manufacture an anode 108 composed of a plate-shaped BDD with a microstructure larger than a certain size.

[0054] To address this issue, conventional methods have been used to manufacture anodes 108 made of large BDDs, such as providing holes or using a mesh-structured substrate. However, these methods have resulted in a large pore area, which increases the area wasted in the manufacturing process of anodes 108 made of BDDs, resulting in increased costs.

[0055] To address this issue, the present invention employs a novel approach: when a large-area anode 108 is required, multiple anodes each made of a small, microstructured BDD are arranged in a circular array. This approach, like disassembling a globe puzzle and arranging it on the floor to create a flat surface, ensures flatness by dividing the BDD into smaller pieces to eliminate the slight curvature caused by heat when fabricating a 1-mm-thick niobium BDD. Furthermore, it allows for the combination of anodes made of BDDs of any desired area while maintaining the benefits of a microstructure. Furthermore, maintaining a distance between anodes made of individual BDDs improves heat dissipation efficiency. Furthermore, the ability to reuse anodes made of identically shaped BDDs for various projects offers significant benefits in terms of production management. As shown in Figure 10, eight anodes 108, each approximately 1 square centimeter in size, are arranged in a ring, preventing the heat-generating surfaces from gathering together, resulting in an electrode configuration with high heat dissipation efficiency.

[0056] In this way, heat dissipation efficiency is taken into consideration in the configuration of the anode 108 itself, but appropriate design is also required for the method of wiring to the anode 108. Depending on the wiring method, the anode 108 may not be able to fully function, so the wiring structure will be explained next.

[0057] Referring to Figure 20, the plate wiring of the comparative example is described. The plate wiring has the problem of impeding the permeation of ozone (O3) through the slit structure 108a of the anode 108. Furthermore, the resistance at the contact points of the plates generates heat. While the plate wiring of the comparative example appears simple and robust at first glance, it has serious practical issues. First, the plate wiring physically obscures the slit structure 108a of the anode 108, blocking the permeation path of ozone (O3). As shown in the figure, if the plate is positioned parallel to the slit structure 108a of the anode 108, the migration of the generated ozone (O3) into the water flow is hindered. Furthermore, although the contact surface between the plate and the anode 108 is large, it is difficult to ensure uniform contact, resulting in localized high-resistance areas. These high-resistance areas generate concentrated heat, leading to deterioration of the contact points and reduced electrode performance. Furthermore, because the plate itself has a large heat capacity, once heat is generated, it takes a long time to cool down, making thermal management of the entire system difficult. These issues impose significant constraints on the performance and reliability of the plate wiring, especially during high-power operation.

[0058] Referring to Figure 21, we will explain wiring using titanium fiber 109 according to an embodiment of the present invention. Fiber wiring provides a stable contact point across the entire anode 108 while maintaining a certain degree of elasticity. Furthermore, its permeable structure allows for ozone (O3) and water (W) to pass through, leveraging the benefits of the slit structure 108a of the anode 108 while minimizing thermal damage. Titanium fiber 109 wiring according to an embodiment of the present invention addresses the problems inherent in plate wiring. Titanium fiber 109 is composed of numerous thin metal fibers that are intertwined in a mesh-like pattern, maintaining a high porosity while maintaining surface contact. This structure allows generated ozone (O3) to pass through the gaps between the fibers and efficiently migrate into the water flow. Furthermore, the elasticity of titanium fiber 109 ensures uniform contact with the surface of the anode 108, reducing contact resistance and achieving uniform current distribution. Furthermore, the fibrous structure provides a large surface area and excellent heat dissipation efficiency, effectively dispersing and releasing heat. Titanium combines high corrosion resistance and electrical conductivity, ensuring long-term stability in ozone (O3) and water environments. This titanium fiber 109 wiring system combines electrical and hydrodynamic performance.

[0059] Referring to Figure 22, we will explain the actual state of multiple anodes 108 arranged on titanium fibers 109. Simply arranging multiple anodes 108 on the titanium fibers 109 enables easy power distribution. Furthermore, ozone (O3) permeates the titanium fibers 109, shattering any remaining dissolved gaseous ozone, which is expected to further increase the dissolution efficiency of ozone (O3). When wiring the anodes 108, if the anodes are installed so that the metal wiring is covered, the metal wiring will not act as an anode. Therefore, depending on the design, water-resistant metals such as stainless steel and even some precious metals can be used, depending on the price. Titanium has excellent corrosion resistance and low conductivity as a metal, with resistance approximately 25 times that of silver. Therefore, the fiber structure according to the present invention achieves efficient power distribution while suppressing heat generation. From the actual image, it can be seen that the titanium fibers 109 uniformly support the multiple anodes 108. The titanium fibers 109 function not only as electrical connections but also as a mechanical support structure. Multiple anodes 108 are arranged in an orderly fashion, with each electrode spaced appropriately. This configuration distributes the water flow evenly, allowing all electrodes to function efficiently. Furthermore, the water flow passing through the gaps in the fiber network creates micro-turbulence, which contributes to the atomization of gaseous ozone and its promotion of dissolution. Although titanium has a relatively low electrical conductivity, the fiber structure increases the contact area, reducing overall electrical resistance. This wiring system is also highly scalable, allowing the number of electrodes to be flexibly adjusted depending on the application.

[0060] 23 to 41, the structure, function, performance comparison with various substrates, and manufacturing process of the porous cation exchange membrane layer 107 (Nafion carbon) according to an embodiment of the present invention will be described.

[0061] FIG. 23 is a diagram showing the component configuration according to an embodiment of the present invention. The left side of FIG. 23 is an exploded view of the entire device, a reprint of FIG. 1. The exploded view on the left side shows, from top to bottom, a waterproof / conductive power supply electrode 101, a holder lid 102, an internal pressure spring 103, a stainless steel cathode 104, a solid acid catalyst cathode 105, a cation exchange membrane 106, a porous cation exchange membrane layer 107, an anode 108, a titanium fiber 109, a holder body 110, and a waterproof / conductive power supply electrode 111. The right side of FIG. 23 is a cross-sectional view of the core components of electrolysis (ozone O3 generation). In this embodiment of the present invention, compared to the comparative example, a porous cation exchange membrane layer 107 (Nafion carbon) is newly provided between the cation exchange membrane 106 and the anode 108. In the cross-sectional view on the right, the components are arranged in order: anode 108, porous cation exchange membrane layer 107, cation exchange membrane 106, solid acid catalyst cathode 105, and SUS cathode 104. A feature of this embodiment of the present invention is the insertion of porous cation exchange membrane layer 107 between cation exchange membrane 106 and anode 108, which dramatically improves the efficiency of ozone water production. While conventional electrolysis cells have limitations in the electrolysis efficiency on the anode side, the introduction of this porous layer significantly increases the effective area of ​​the electrolysis reaction field, improving electrolysis efficiency. This structure also optimizes water flow distribution within the electrolysis cell and contributes to improved thermal management. These synergistic effects enable this embodiment of the present invention to achieve 1.5 to 2 times the efficiency of conventional ozone water production with the same input power.

[0062] The configuration of the comparative example will be described with reference to Figure 24. In this comparative example, the porous cation exchange membrane layer 107 is not provided, and the cation exchange membrane 106 is in direct contact with the anode 108. In this configuration, the smooth membrane structure limits the electrolysis efficiency. In the comparative example, the cation exchange membrane 106 and the anode 108 are in direct contact, so the electrolysis reaction occurs only at the planar interface between them. This planar electrolysis reaction field limits the effective surface area, limiting the electrolysis efficiency. Furthermore, if minute gaps form between the cation exchange membrane 106 and the anode 108, incomplete electrical contact occurs, resulting in localized high-resistance regions. Heat is concentrated in these regions, causing membrane degradation and performance degradation. Furthermore, the planar structure tends to result in uneven water flow distribution, which reduces the ozone O3 dissolution efficiency and heat dispersion. The supply of water required for the electrolysis reaction is also limited, potentially resulting in performance degradation due to water shortages during high-current-density operation. Due to these constraints, the configuration of the comparative example has limitations in power efficiency and long-term stability, making it difficult to efficiently generate high-concentration ozone water.

[0063] With reference to Figure 25, the structural change of the porous cation exchange membrane layer in the initial stage of ozone O3 generation will be described. When carbon fibers are coated with Nafion, the carbon (C) in the Nafion carbon loses electrons e (e-) in the anodic reaction and is converted into CO2. This can also be expressed as the carbon fibers being corroded by the anodic reaction. The initial state of the porous cation exchange membrane layer 107 is a composite structure in which the carbon fibers are coated with Nafion resin. When electrolysis begins, electrons are lost from the carbon fibers in the anodic reaction, and an oxidation reaction progresses. This oxidation reaction gradually converts the carbon fibers into carbon dioxide (CO2). This process is represented by the following chemical reaction equation: C + 2H2O → CO2 + 4H ++ 4e-. This reaction proceeds in stages, with oxidation progressing from the surface of the carbon fiber to its interior. At this early stage, the carbon fiber has not yet completely disappeared, and some remains. This gradual oxidative removal of the carbon fiber is the precursor to the formation of porous or capillary water channels, which will be described later. This process also functions as a "break-in" for the electrolytic cell, resulting in a gradual improvement in electrolytic efficiency.

[0064] Referring to FIG. 26 , the formation of cavities 127 after removing the carbon fibers will be described. When the carbon fibers are converted to CO2, cavities 127 form in the locations where the carbon fibers were present, forming water-permeable spaces. As the electrolysis progresses, the carbon fibers are completely oxidized, forming cavities 127 in their original positions. These cavities 127 form fine tubular structures corresponding to the original shape of the carbon fibers. These cavities 127 fill with water to form water-permeable spaces. These water-permeable spaces form interconnected three-dimensional networks that function as water passageways. The structural characteristics of the water-permeable spaces 128 formed are determined by the thickness, orientation, and density of the carbon fibers. An optimal network of water-permeable spaces 128 can be achieved by properly designing the carbon fiber arrangement. This cavity formation process can be considered a self-organizing property of the porous cation-exchange membrane layer or Nafion carbon 107 according to an embodiment of the present invention, and is a unique function that gradually forms an optimal structure during use.

[0065] The function during the ozone O3 generation stage will be described with reference to Figure 27. The water flow space 128, also shown in Figure 26, is filled with water W, forming a porous structure similar to a Nafion membrane. This flexibility of the Nafion membrane enhances its conformability (adhesion) to the anode 108, resulting in an increased amount of water supplied to the electrolysis surface. The water flow space 128 formed by removing the carbon fibers functions as a porous network filled with water W. This porous structure surrounded by the Nafion material efficiently draws in water W through capillary action, providing a stable supply of the water necessary for the electrolysis reaction. Furthermore, because the Nafion material itself is flexible, the presence of the water flow space 128 improves the overall elasticity and enhances its adhesion to the anode 108 surface. This improved adhesion results in uniform electrical contact and improved electrolysis efficiency. Furthermore, this water supply network contributes to the dispersion of heat generated during the electrolysis reaction, improving temperature control throughout the electrolysis cell. The constant supply of fresh water through the water passage space 128 prevents the accumulation of reaction products, enabling sustained, highly efficient electrolysis. This porous network structure supports the functionality of the porous cation exchange membrane layer 107 according to an embodiment of the present invention.

[0066] The effect of the porous cation-exchange membrane layer 107 is explained with reference to Figure 28. The numerous three-interfaces 126 (described later) that cannot be created with a smooth Nafion membrane are secured, which is expected to improve electrolysis efficiency. The Nafion felt formed by carbon loss has a fine structure that causes wear over long periods of use. However, after wear, the Nafion membrane itself comes into direct contact with the anode 108. A significant effect of the porous cation-exchange membrane layer 107 is the increase in the number of "three-interfaces 126" in the electrolysis reaction. The three-interface 126 is the interface where the electrode, electrolyte, and water come into contact, and is where the electrolysis reaction proceeds most efficiently. In conventional smooth Nafion membrane structures, these three-interfaces 126 are formed only in a limited planar area. However, with a porous structure, countless three-interfaces 126 are formed throughout the entire porous network, expanding the electrolysis reaction field. This allows for high electrolysis efficiency even with the same electrode area. Even if the porous structure wears and deteriorates over time, the Nafion membrane itself will eventually come into direct contact with the anode 108, maintaining performance equivalent to that of conventional structures. In other words, the design incorporates a fail-safe mechanism for performance degradation. Furthermore, when the carbon fibers are completely removed, the structure remains pure Nafion, eliminating the risk of foreign matter contamination.

[0067] The relationship between the cathode, Nafion membrane, and anode will be described with reference to Figures 29 to 31. Figure 29 shows the relationship between the solid acid catalyst cathode 105, cation exchange membrane (Nafion membrane) 106, porous cation exchange membrane layer (Nafion carbon) 107, and anode 108. Figure 30 is an enlarged view of the area surrounded by the dashed-dotted line in Figure 29, and shows the formation of three interfaces when Nafion carbon is used. Figure 31 shows the formation of three interfaces in a comparative example. Although the term "electrolytic surface" is often used, in reality, it is a surface with countless electrolytic points (three interfaces 126) scattered throughout, and electrolysis does not occur at all points on the electrolytic surface 125.

[0068] Here, the three-interface 126 refers to the interface where the anode 108 and water W are in contact and the cathode 104 is located nearby. The key to understanding the nature of electrolysis is the fact that the reaction does not occur uniformly across the entire surface but rather occurs intensively at specific "points." These electrolysis points are formed at locations called "three-interfaces 126" where the electrode (anode 108 or cathode 104), electrolyte, and reactant (water W) come into contact. At these three-interfaces 126, electron transfer, ion conduction, and reactant supply occur simultaneously, maximizing the efficiency of the electrolysis reaction. As shown in the figure, in a simple stacked structure of the anode 108, cation exchange membrane (Nafion membrane) 106, and cathode 104, the three-interface 126 is primarily limited to the edges of the materials and minute contact points. This is the factor limiting the efficiency of the planar electrolysis cell in the comparative example. In the present embodiment, the introduction of a porous cation exchange membrane layer (Nafion carbon) 107 dramatically increases the number of these three-interfaces 126, thereby improving electrolysis efficiency.

[0069] Referring to Figure 30, the formation of three interfaces 126 when using Nafion carbon will be described. The porous cation-exchange membrane layer 107 has a porous structure. Water W flows through the Nafion membrane and contacts the anode 108 at many interfaces. These many interfaces form three interfaces 126, and electrolysis occurs at many interfaces. For this reason, it is important to miniaturize the water channels 112, and the porous cation-exchange membrane layer 107 fulfills this function. When using a porous cation-exchange membrane layer 107 or a Nafion carbon membrane, water W flows through the porous water channels 112 formed therein. This water W reaches the contact point between the wall of the water channel 112 (Nafion material) and the anode 108, forming countless three interfaces 126. As shown in the figure, numerous three interfaces 126 are distributed throughout the porous network, and these simultaneously function as electrolytic reaction sites. In this structure, the electrolytic reaction unfolds three-dimensionally, increasing the effective reaction area. By optimizing the diameter, density, and orientation of the porous structure, it is possible to control the formation of the three interfaces 126, thereby further improving efficiency. The network structure of the water channels 112 also improves the efficiency of the discharge of reaction products and the supply of fresh reactants. These factors work in combination to achieve high ozone water production efficiency in the electrolytic cell according to the embodiment of the present invention.

[0070] The formation of the three interfaces 126 in the comparative example will be described with reference to Figure 31. It can be seen that the number of three interfaces 126 in the comparative example is very small and limited. This significantly limits the electrolysis efficiency. In the conventional planar structure, the contact between the cation exchange membrane 106 and the anode 108 is essentially planar, and the three interfaces 126 are limited to the boundary between them and minute surface irregularities. As shown in the figure, the number of three interfaces 126 in the comparative example is extremely small, limiting the electrolysis reaction field. Planar contact is prone to tiny gaps and poor contact areas between the Nafion membrane and the electrode, creating "dead space" where the electrolysis reaction does not occur. Furthermore, if gases (such as ozone O3) generated by the electrolysis reaction remain at the interfaces, this further inhibits the electrolysis reaction. The planar structure also makes the supply and discharge of water inefficient, easily resulting in a lack of reactants and the accumulation of products. Due to these limitations, the conventional structure has a low electrolysis efficiency relative to the input power, making it difficult to efficiently generate high-concentration ozone water. In comparison with the porous structure according to the embodiment of the present invention, it can be seen that the formation of the three interfaces 126 in the conventional structure is restricted.

[0071] With reference to FIG. 32, the effect of improving water flow efficiency according to an embodiment of the present invention will be described. One advantage of generating ozone O3 through electrolysis is the possibility of generating high-concentration ozone O3. To achieve this, approximately 10 W of power is applied to an electrolysis area of ​​approximately 1 square centimeter. However, because not all of the applied power energy is used for electrolysis, the temperature of the electrolysis surface 125 rises. In an embodiment of the present invention, water flow improves heat dissipation efficiency, thereby suppressing the temperature rise of the electrolysis surface 125. An important secondary effect of the porous cation exchange membrane layer 107 is improved thermal management within the electrolysis cell. High-concentration ozone water generation requires high-power-density operation, and the associated heat generation is a major cause of performance degradation. The porous network formed within the porous structure according to an embodiment of the present invention enables efficient water circulation, which functions as a natural water cooling system. As shown in the figure, water W flowing through the water passage 112 efficiently absorbs and releases heat from the electrolysis surface 125, suppressing temperature rise. In conventional flat structures, the water flow only comes into contact with a portion of the electrode surface, whereas in porous structures, the water flow is distributed three-dimensionally, ensuring a larger heat exchange area. In addition, the fine water flow has a turbulent component, further improving heat transfer efficiency. Suppressing temperature rise also directly contributes to suppressing the decomposition of ozone O3, which ultimately contributes to improving the concentration of ozone water. This improvement in heat dissipation efficiency also plays an important role in improving the long-term stability and durability of the electrolysis cell.

[0072] Referring to Figure 33, the high-temperature problem in the comparative example will be explained. The higher the temperature, the faster the decomposition rate of ozone O3. The higher the concentration of ozone O3, the faster the decomposition rate. Therefore, high temperature and high concentration conditions are conditions that favor ozone O3 decomposition. In the comparative example, the water flow efficiency is poor, making ozone O3 decomposition more likely at high temperatures. With the planar structure of the comparative example, the cooling effect of the water flow is limited, resulting in a significant temperature rise on the electrolysis surface. As shown in the figure, high-temperature areas (dark gray areas) are widely formed on the electrode surface, causing rapid decomposition of ozone O3. With a planar structure, the water flow distribution is prone to be uneven, resulting in water stagnation and a decrease in flow rate, especially in the center. Heat accumulates in these areas, forming localized high-temperature areas (hot spots). At high temperatures, the self-decomposition reaction of ozone O3 is accelerated, increasing the rate at which the generated ozone O3 decomposes back into oxygen. This phenomenon is particularly pronounced under high-concentration ozone conditions, resulting in a significant decrease in production efficiency. Furthermore, high temperature conditions accelerate the degradation of electrode materials and Nafion membranes, shortening the lifespan of electrolysis cells. These issues are the main causes of the performance limitations of conventional structures. The improved thermal management achieved by the porous structure according to the embodiments of the present invention is a technology that solves these problems.

[0073] Various materials can be used as the substrate 118 of the porous cation exchange membrane layer 107. Here, specific examples of components other than carbon fiber that can be expected to improve electrolytic efficiency will be described below with reference to Figures 34 to 46.

[0074] Materials used for the substrate 118 are roughly classified into organic hydrophilic materials, inorganic hydrophilic materials, hydrophobic materials, and conductive materials. The characteristics of each will be explained below.

[0075] Examples of organic hydrophilic materials include cellulose nonwoven fabric (cupra). Unlike carbon fiber, it does not have the characteristic of instantly decomposing to form water channels 112, but the micro-wrinkles and porous microstructure of the substrate 118 provide an effect similar to that of a carbon substrate. An advantage is that ozone (O3) is generated immediately, as carbon does not temporarily act as an electrode like a carbon substrate. A disadvantage is that the voltage is somewhat higher due to the passive layer.

[0076] Examples of inorganic hydrophilic materials include glass fiber. The fiber structure of the substrate 118 creates countless minute irregularities, which can produce an effect similar to that of a carbon substrate. However, if the glass fiber has a large exposed surface area, it may react in a way that reduces the ozone O3 concentration, so care must be taken when handling it. An advantage is that glass is more ozone-resistant than materials such as cellulose, making it easier to maintain stability after formation. Disadvantages include the possibility of a decrease in the ozone O3 concentration and concerns about the glass shattering.

[0077] Examples of hydrophobic materials include fluoropolymer fibers. The substrate 118 has fine irregularities and has a similar structure to the two examples above, but the exposed parts of the substrate 118 have a water-repellent effect, which causes bubbles to adhere during electrolysis, reducing efficiency. Advantages can be obtained by combining it with hydrophilic materials such as the two examples above. Advantages include the fact that there is no need to worry about shattering or decomposition and loss, making it the most stable substrate 118. Disadvantages include the fact that due to its hydrophobic nature, it is necessary to form a hydrophilic layer.

[0078] Examples of conductive materials include metal fibers. These are generally unsuitable because they react preferentially with the boron-doped diamond electrode due to their location. Carbon fibers are also unsuitable for the same reason, but they turn into CO2 and scatter, so no ongoing problems can occur. However, the risk of residual metal cannot be completely ruled out, so it is best to avoid using conductive materials.

[0079] Figure 34 shows a cupra element. Cellulose nonwoven fabric (cupra), an organic fiber material, is not conductive and therefore does not function as an electrode. Unlike carbon fibers, however, it does not instantly disappear and form water channels 112. However, the fibers are aggregated into a "wirl" structure, resulting in numerous irregularities and water channels 112 within the wirl. Furthermore, cellulose itself is highly hydrophilic, which allows for water retention and water permeability. Furthermore, over time, cellulose is decomposed by ozone (O3), forming water channels 112. Cupra elements have a "wirl" structure, consisting of bundles of fibers. This structure itself forms a network of fine water channels 112. As shown in the figure, multiple cellulose fibers are intertwined, creating natural voids between them. Cellulose is inherently hydrophilic, and the hydroxyl groups (-OH) present on its surface form hydrogen bonds with water molecules. This allows cupra fibers to quickly absorb and efficiently retain water. Furthermore, cellulose is slowly oxidized and decomposed by ozone O3, so over long-term use, the fibers gradually decompose, forming wider water channels 112. This "self-optimizing over time" property is a unique advantage of the cupra substrate 118. Due to the natural properties of cellulose, it is also environmentally and biocompatible, and is advantageous from a safety perspective.

[0080] Figure 35 shows the state of cupra coated with Nafion. A Nafion coating is applied to the surface of a cupra substrate 118, forming a porous structure. The figure shows the cupra fiber surrounded by Nafion resin. The thickness of the Nafion coating is optimized to maintain the fiber shape while ensuring ionic conductivity. Even after coating, the voids between the fibers remain, functioning as water channels 112. The Nafion coating gives the cupra fiber proton conductivity and allows it to function as an electrolyte. This composite structure combines the hydrophilicity and water retention properties of cupra with the ionic conductivity of Nafion, making it an excellent functional material. The final porous structure characteristics can be controlled by adjusting the coating process conditions.

[0081] Figure 36 shows the water flow state of cupra. Both the water flow channels 112 formed by the unevenness and the water flow channels 112 within the fiber bundle function effectively, achieving efficient water flow. In the porous cation exchange membrane layer 107 using cupra substrate 118, two types of water flow channels 112 are formed: surface water flow channels formed by the fine unevenness of the fiber surface, and internal water flow channels formed within the fiber bundle (ply). As shown in the figure, these water flow channels 112 form an interconnected network, enabling efficient water movement. The surface water flow channels are primarily responsible for supplying water to the electrolysis surface 125 and discharging the product, while the internal water flow channels are responsible for retaining and gradual supply of water. This dual water flow mechanism maintains a stable water supply even in the face of rapid fluctuations in water flow. The excellent capillary action of cupra allows water to spontaneously move within the water flow channels 112, constantly supplying the moisture necessary for the electrolysis reaction. The hydrophilic surface of cupra also promotes the dissolution of the generated ozone O3. This multi-layered water permeability mechanism is the basis for the excellent performance of the porous cation exchange membrane layer 107 using the cupra substrate 118.

[0082] Figure 37 shows actual images of the Nafion felt with cupra substrate 118 before and after electrolysis. The images show the state before and 10 hours after electrolysis, revealing traces of decomposition in the Nafion felt with cupra substrate 118. Over time, cellulose is decomposed by ozone O3, presumably forming water channels 112. The left side of the image shows the state before electrolysis, clearly showing the fibrous structure of the cupra substrate 118. Meanwhile, the right side, an image taken 10 hours after electrolysis, shows changes in the fibrous structure, with partial decomposition and discoloration evident. These changes indicate the oxidative decomposition of cellulose by ozone O3. Ozone O3 breaks the molecular chains of cellulose, gradually breaking it down into smaller molecules. This decomposition process progresses from the surface to the interior, expanding the water channels 112 over time. Furthermore, the oxidized cellulose fragments produced by the decomposition process become water-soluble and are expelled from the system by the water flow. The development of this "self-forming" water channel structure results in improved performance over time in the electrolysis cell. This process is unique to cupro substrates and proceeds through a different mechanism than the electrochemical oxidation of carbon fibers.

[0083] Figure 38 shows a performance comparison table between the cupra product and existing products. The table shows the results of comparing the conductivity and ozone O3 concentration of Nafion felt with a cupra nonwoven fabric substrate 118 with existing products. The cupra product tends to have a slightly higher voltage, but the higher ozone O3 concentration reduces the calculated power required to output 1 mg / L. The cupra product consumes 11.7 W, while the existing product consumes 14.4 W, resulting in greater power savings (higher efficiency). Regarding voltage, since cupra itself is an insulator with a porous structure, some of it may obstruct ion conduction. The degree of this obstruction is presumably dependent on the pore ratio and thickness of the cupra. The performance comparison table demonstrates the superiority of the porous cation exchange membrane layer 107 using the cupra substrate 118. The cupra product achieves a high ozone concentration of 0.9 mg / L, a 50% improvement over the existing product's 0.6 mg / L. In terms of voltage, the cupra product showed a slightly higher value of 8.8V, but even taking this voltage increase into account, the effect of improving ozone concentration was more pronounced. In terms of the efficiency index, "power required for 1 mg / L," the cupra product required 11.7W, while the conventional product required 14.4W, achieving a power saving of approximately 19%. This efficiency improvement is thought to be due to the excellent moisture supply capacity of the cupra base material 118 and the effect of forming three interfaces 126. The reason for the voltage increase is thought to be that the cupra fiber itself is an electrical insulator, which partially restricts the ion conduction path. However, this voltage increase is not enough to offset the benefits of the improved ozone concentration, and overall efficiency is improved.

[0084] Figure 39 shows the time-dependent changes in ozone O3 concentration for the cupra and conventional products. While the cupra product initially has a higher concentration than the conventional product, the difference tends to decrease over time, making sustainability the next challenge. The table clearly shows the differences in the time-dependent characteristics of the cupra and conventional products. At the start of the experiment, the cupra product had a high ozone O3 concentration compared to the conventional product, at 0.9 mg / L, while the conventional product had a high ozone O3 concentration of 0.6 mg / L. However, the difference narrowed over time. After 24 hours, the cupra product had a high ozone O3 concentration compared to the conventional product, at 0.8 mg / L and 0.6 mg / L, respectively. After 40 hours, the two products were roughly equivalent at 0.8 mg / L and 0.7 mg / L, respectively. After 100 hours, the difference narrowed even further, with the cupra product at 0.7 mg / L and the conventional product at 0.6 mg / L. This pattern of change over time is thought to reflect the gradual changes in the cupra substrate 118. In the initial stage, high ozone generation efficiency is achieved due to cupra's excellent water retention and porous structure. However, over time, ozone (O3) decomposes the fibers, causing the structure of the water channels 112 to change. Over the long term, the structure gradually changes due to partial loss of the cupra fibers, and the performance characteristics tend to converge to those of existing products. This change over time is an important consideration in the lifespan design of the porous cation exchange membrane layer 107 using the cupra substrate 118.

[0085] Figure 40 is a performance comparison table for glass fiber substrates. The table shows the results of comparing electrical conductivity and ozone O3 concentration using Nafion felt with existing products, using glass fiber as the substrate 118. It was confirmed that the results varied depending on conditions such as the fiber diameter. A general trend was observed for glass fiber, with larger fiber diameters resulting in higher voltage and ozone O3 concentration. However, increasing voltage beyond a certain level is likely to place a heavy burden on surrounding materials such as the Nafion membrane, making it unsuitable for this purpose in terms of lifespan. Furthermore, glass has many -SiOH (silanol) groups or -OH (hydroxyl) groups on its surface, which can potentially act as adsorbents or decomposition catalysts for ozone O3. The narrow fiber diameter (i.e., large surface area) increases the probability of contact with ozone O3, which is thought to be a factor in the above trend. The performance comparison table clearly shows that performance characteristics vary significantly depending on the diameter of the glass fiber substrate 118. The 6 μm diameter glass fiber exhibits a relatively low ozone concentration of 0.5 mg / L and a moderate voltage of 9.2 V. At 11 μm diameter, the ozone concentration increased to 0.8 mg / L, and the voltage also increased slightly to 9.9 V. At 18 μm diameter, the ozone concentration increased further to 1.1 mg / L, but the voltage also increased significantly to 11.8 V. Comparing the efficiency index (power required for 1 mg / L) for the 6 μm diameter, the results are 22.1 W for the 6 μm diameter, 14.9 W for the 11 μm diameter, and 12.9 W for the 18 μm diameter. The efficiency improves with increasing fiber diameter. The main reason for this trend is thought to be that the shape and distribution of the water channels 112 are optimized with a larger fiber diameter, resulting in efficient water supply and the formation of three interfaces 126. On the other hand, the increased surface area of ​​thinner fibers may enhance the ozone (O3) decomposition effect due to silanol groups and other factors. However, an increase in voltage leads to increased heat generation and material deterioration in the electrolysis cell, so the balance between efficiency and lifespan must be considered when selecting the fiber diameter.

[0086] Figure 41 shows a performance comparison table of the PTFE nonwoven fabric substrate 118. The Nafion felt with the PTFE substrate 118 exhibited low ozone O3 concentrations and high voltages, making it the least efficient of the samples tested. The power required for 1 mg / L was 72.0 W for the PTFE substrate and 14.4 W for the conventional product. The performance comparison table clearly shows the performance characteristics of the porous cation exchange membrane layer 107 using the PTFE substrate 118. The Nafion felt with the PTFE substrate 118 exhibited an ozone concentration of 0.4 mg / L, approximately 33% lower than the 0.6 mg / L of the conventional product, and the voltage was 24.0 V, more than 3.3 times higher than the 7.2 V of the conventional product. As a result, the efficiency index, "power required for 1 mg / L," was 72.0 W for the PTFE substrate 118, consuming approximately five times more power than the 14.4 W of the conventional product. This significant performance decline is due to the strong hydrophobicity of PTFE, which creates unfavorable conditions for both water supply and product discharge during the electrolysis reaction. PTFE is a desirable material from the standpoint of excellent chemical stability and durability, but its use alone has been shown to significantly reduce electrolysis efficiency. These results demonstrate that hydrophilicity is an extremely important factor in selecting the substrate 118 for the porous cation-exchange membrane layer 107.

[0087] Figure 42 shows the phenomenon of air bubbles adhering to the PTFE substrate 118. It is believed that the highly hydrophobic PTFE exposed from the Nafion coating traps and adhering gases (such as ozone O3) continuously generated by electrolysis, inhibiting ion conduction. This phenomenon is believed to be the cause of the poor performance of the PTFE substrate 118. As shown in Figure 42, in the porous cation exchange membrane layer 107 of the PTFE substrate 118 disposed between the anode 108 and the cathode, air bubbles adhering to the PTFE fiber surface exposed from the Nafion coating occur. PTFE has a highly hydrophobic contact angle with water of approximately 110° or more, so gas molecules such as ozone O3 and oxygen generated during the electrolysis reaction easily adhere to the fiber surface, and once attached, they are not easily removed. These adhering air bubbles physically block the ion conduction pathway and also obstruct the water W supply pathway. As a result, the supply of water (W) required for the electrolysis reaction becomes insufficient, and the movement of ions generated by electrolysis is also hindered, causing a rise in voltage and a decrease in the efficiency of ozone (O3) generation. In particular, the voltage rise was extremely high at 24.0 V, indicating a significant decrease in the ion conduction path. This bubble adhesion phenomenon tends to increase as electrolysis progresses, and is a factor that further exacerbates the performance decline during long-term operation.

[0088] Figure 43 shows the structure of a PTFE + cupra composite substrate 118. A PTFE and cupra composite sample was created with the cupra positioned on the anode-contact surface to maintain hydrophilicity and prevent air bubbles from reaching the PTFE fibers. Because cupra is hydrophilic, generated air bubbles flow away without adhering. As shown in Figure 43, this composite substrate 118 employs a laminated structure with a cupra layer on the anode 108 side and a PTFE layer on the solid acid catalyst cathode 105 side. This structure aims to prevent the air bubble adhering phenomenon shown in Figure 42 by making the surface in contact with the anode 108 hydrophilic cupra. Cupra is a cellulose-based hydrophilic material with a low contact angle with water (approximately 20-30°) and a high affinity for water (W). Therefore, air bubbles generated during the electrolytic reaction flow away without adhering to the cupra surface, ensuring ion conduction and water supply paths. On the other hand, the PTFE layer has excellent ozone resistance and chemical stability, and by placing it on the solid acid catalyst cathode 105 side, it serves to increase the durability of the entire composite substrate 118. This layered structure is expected to eliminate the drawback of PTFE alone, which is the adhesion of air bubbles, while complementing the insufficient durability of cupra alone. As shown in the figure, the cupra fibers and PTFE fibers are not arranged alternately, but form a distinct layer structure, which makes it possible to maximize the properties of each material.

[0089] Figure 44 is a table showing the performance of the PTFE + cupra substrate 118. The Nafion felt with the PTFE + cupra substrate 118 exhibited a significantly lower voltage than the Nafion felt with PTFE alone. This suggests that the PTFE substrate 118 itself does not increase the voltage, but rather that the electrolysis efficiency is significantly affected by its surface condition. The Nafion felt with this composite substrate 118 exhibited an ozone concentration of 0.7 mg / L, a 75% improvement over the 0.4 mg / L achieved with PTFE alone. Another significant improvement was a 50% reduction in voltage, from 24.0 V to 12.1 V. As a result, the efficiency index, "power required for 1 mg / L," also improved significantly from 72.0 W with PTFE alone to 20.7 W. This performance improvement is due to the hydrophilic effect of the cupra layer located on the anode 108 side, demonstrating the provision of water W necessary for the electrolysis reaction and the establishment of an ion conduction path. However, the efficiency was still lower than that of existing products (20.7 W vs. 14.4 W), suggesting that some resistance due to the presence of the PTFE layer remains. However, this composite substrate 118 configuration significantly improves the problems associated with using PTFE alone and may offer greater durability than cupra alone. These results highlight the importance of optimizing both the material selection and structural design of the substrate 118.

[0090] Figure 45 illustrates the relationship between current and voltage during electrolysis. The amount of electrolysis product (in this embodiment, the amount of ozone (O3), oxygen, hydrogen, etc.) is roughly determined by the amount of electricity, which is calculated using Faraday's law (amount of electricity = current × time). The voltage is a value output to ensure a specified current and is not generally proportional to the amount of electricity (≒ amount of product). The current represents the number of electrons (e) exchanged per second during electrolysis, and therefore essentially represents the amount of product. Figure 45 explains the basic electrochemical behavior of the electrolysis cell 1. The anode 108 is shown on the left side of the figure, the solid acid catalyst cathode 105 is shown on the right, and the cation exchange membrane 106 is located in the center. During the electrolysis reaction, the anode 108 removes electrons (e) from water molecules to produce oxygen or ozone (O3). The dissociated hydrogen ions (H) pass through the cation exchange membrane 106 and migrate to the solid acid catalyst cathode 105, where they receive electrons (e) and become hydrogen gas. The arrows in the diagram indicate the flow of electrons e and the movement of ions. The current value represents the amount of electrons e moved and, according to Faraday's law, is directly related to the amount of product. On the other hand, voltage represents the energy required for the movement of electrons e and the transport of ions, and is greatly affected by the internal resistance of the electrolytic cell 1. The internal resistance varies depending on various factors, such as the state of the porous cation exchange membrane layer 107 and the cation exchange membrane 106, the state of contact with the electrodes, and even the conductivity of the electrolyte. For this reason, voltage is not directly proportional to the amount of product, but is an important indicator for evaluating the efficiency and condition of the electrolytic cell 1. The lower the voltage, the less energy is consumed to obtain the same current (i.e., the same amount of product), indicating higher efficiency.

[0091] Figure 46 shows the correlation between current value and ozone concentration, voltage, and amount of hydrogen produced during electrolysis. The results are shown for the comparative example and a glass fiber substrate 118 (fiber diameter 18 μm) measured under two conditions: current values ​​of 1.2 A and 1.8 A. In the comparative example, at a current value of 1.2 A, the ozone concentration was 0.7 mg / L, the voltage was 7.5 V, and the amount of hydrogen produced was 10 mL / min. When the current value was increased to 1.8 A, the ozone concentration rose to 1.2 mg / L, the voltage also rose slightly to 8.9 V, and the amount of hydrogen produced rose to 15 mL / min. Similarly, with the glass fiber substrate 118, the ozone concentration (1.1 mg / L to 1.6 mg / L), the voltage (11.8 V to 12.4 V), and the amount of hydrogen produced (10 mL / min to 15 mL / min) all increased with an increase in current value. Of particular note is the increase in the amount of hydrogen produced in proportion to the current value (1.5 times from 1.2 A to 1.8 A), which is consistent with the theoretical prediction based on Faraday's law. Meanwhile, the rate of increase in ozone concentration varied depending on the material, with a 1.7-fold increase in the comparative example and a 1.45-fold increase in the glass fiber substrate 118. These results demonstrate that in designing the electrolysis cell 1, it is important not only to control the current value, but also to improve the ozone (O3) generation efficiency and dissolution efficiency by selecting the right material for the porous cation exchange membrane layer 107 and optimizing its structure.

[0092] This comparative study of different anode materials was conducted at a current of 1.2 A. If current is taken to be approximately equal to product, then there should be little difference in product yield. However, a certain difference was observed depending on the anode material (0.4–1.1 mg / L; control: 0.6 mg / L). This difference is due to the fact that ozone (O3) is an oxygen allotrope and converts to oxygen depending on the conditions. Furthermore, ozone (O3) is a gas at room temperature and pressure, so dissolution efficiency influences the product yield. Since measuring the concentration of ozone (O3) in a water-dissolved state is not appropriate for determining the relationship between product yield and current, we utilized the characteristics of our hydrogen separation electrolysis cell 1 to measure the current and the amount of hydrogen gas generated to confirm the discrepancy between theoretical and actual values. Hydrogen gas is less soluble in water than ozone (O3) and does not convert to an allotrope, providing a more direct indicator. Figure 46 shows that for the two anode materials compared, the amount of hydrogen gas generated was 1.5 times greater at currents of 1.2 A and 1.8 A, demonstrating a nearly proportional relationship. This indicates that electrolysis cell 1 functions accurately in accordance with Faraday's law. The reason why the change in ozone O3 concentration is not as precisely proportional to the current value as the amount of hydrogen generated is due to the complex processes of ozone O3 generation, dissolution, and decomposition.

[0093] In this experiment, the total amount of electrons transferred was almost the same for different anode materials. Therefore, we speculate that the differences in the concentration of dissolved ozone (O3) depended on whether the anode product at the time of measurement was ozone (O3) or oxygen, and the extent to which the vaporization and dispersion rates differed. When operated at the same current, the same amount of hydrogen ions (H) were reduced to hydrogen gas on the cathode side, resulting in a nearly constant amount of hydrogen production. Meanwhile, on the anode (108), oxygen and ozone (O3) were produced by the oxidation reaction of water (W). However, the production ratio depends on several factors, including the catalytic activity of the anode (108), the local current density, and the water (W) supply. For example, if the porous cation exchange membrane layer (107) efficiently supplies water (W) and contributes to the formation of the three-interface (126), the production ratio of ozone (O3) may increase. Furthermore, the efficiency with which the generated ozone (O3) dissolves in water (W) also varies depending on the material. A highly hydrophilic substrate (118) increases the contact area with water (W), potentially improving the dissolution efficiency of ozone (O3). Conversely, in the case of a highly hydrophobic PTFE substrate 118, the generated ozone O3 may adhere as bubbles or contact with the water W may be restricted, resulting in a decrease in dissolution efficiency.

[0094] An objective of the present invention is to realize that by arranging a more suitable anode material in ozone (O3)-producing electrolysis, ozone water may be produced more efficiently (by delaying the oxygenation of ozone (O3) and providing a structure that is efficient for dissolution) than by simply placing the anode 108 and cation exchange membrane 106 adjacent to each other. From this perspective, the present invention improves electrolysis efficiency by incorporating a porous cation exchange membrane layer 107. It is important to emphasize here that the introduction of the porous cation exchange membrane layer 107, which is the core of the present invention, is not simply an additional material but a structural innovation that improves the efficiency of the entire electrolysis system. As shown in Figures 23 to 28, the porous cation exchange membrane layer 107 is disposed between the cation exchange membrane 106 and the anode 108 and has porous water channels 112, which optimize the supply of water (W) required for the electrolysis reaction and promote the efficient dissolution and transport of the generated ozone (O3). In the configuration of the comparative example, the smooth cation exchange membrane 106 was in direct contact with the anode 108, which restricted the supply of water W and the movement of the product, resulting in reduced electrolysis efficiency. In contrast, the porous cation exchange membrane layer 107 according to the embodiment of the present invention forms a network of fine water channels 112 and creates a large number of three interfaces 126 (contact points between water W, the anode 108, and the ion conduction path), thereby significantly increasing the active sites for the electrolysis reaction. Furthermore, this structure also promotes efficient heat removal from electrolysis and has the effect of suppressing the thermal decomposition of ozone O3. Due to these combined effects, the ozone water generator according to the embodiment of the present invention is able to generate ozone water more efficiently than the comparative example.

[0095] A continuous cation discharge system using a solid acid catalyst cathode 105 according to an embodiment of the present invention will be described with reference to Figs. 47 to 66. Fig. 47 is a diagram showing the permeation of hardness components (metal cations) through an ion exchange membrane. Fig. 48 is a diagram showing passivation by deposition of metal cations in the cathode. Fig. 49 is a diagram showing continuous cation discharge according to an embodiment of the present invention. These figures explain the metal ion discharge mechanism using the solid acid catalyst cathode 105, which is another important technical feature according to an embodiment of the present invention.

[0096] As shown in Figure 47, hardness components (mainly metal cations such as calcium and magnesium) contained in raw water W are dissolved in the water W in an ionic state. During the electrolysis process, these metal cations are influenced by the electric field and permeate the cation exchange membrane 106, migrating toward the cathode 104. The diagram shows the migration path of calcium ions (Ca2+) as an example. The cation exchange membrane 106 has a polymer structure with sulfonic acid groups (SO2-), which allows the selective permeation of cations.

[0097] Figure 48 illustrates a problem with the comparative example. In the configuration of the comparative example, metal cations that permeate the cation exchange membrane 106 receive electrons e on the surface of the cathode 104 and precipitate as metal or hydroxide. This precipitate forms an electrically insulating passive layer, gradually reducing the effective area of ​​the cathode 104. As a result, the electrolysis efficiency decreases, and this may ultimately lead to the electrolysis cell 1 ceasing to function.

[0098] Figure 49 illustrates a solution using a solid acid catalyst cathode 105 according to an embodiment of the present invention. In this embodiment, the solid acid catalyst cathode 105 is placed between the cation exchange membrane 106 and the cathode 104 to control the deposition location of metal cations. The solid acid catalyst cathode 105 is made of a material with sulfonic acid groups, similar to the cation exchange membrane 106, and provides a path for the metal cations to migrate. However, because the solid acid catalyst itself does not possess electrons e, the metal cations are not reduced here. Instead, they eventually reach the surface of the cathode 104, where they receive electrons e and deposit. Furthermore, hydrogen gas bubbles generated at the cathode 104 mechanically peel off the deposited metal ions and eject them outside the electrolysis cell 1. The figure shows calcium precipitates P, represented by cubes, being continuously ejected. This mechanism prevents passivation of the cathode 104 surface, enabling stable electrolysis performance to be maintained over a long period of time.

[0099] The principle of cation discharge using a solid acid catalyst will be described with reference to Figures 50 to 55. Figure 50 is a diagram showing the relationship between a cation exchange membrane 106, a solid acid catalyst cathode 105, and a cathode 104. Figure 51 is a diagram showing the structure of the solid acid catalyst cathode 105. These figures explain the structure and operating principle of the solid acid catalyst cathode 105 in more detail.

[0100] Figure 50 shows the arrangement of the solid acid catalyst cathode 105 in the electrolysis cell 1. The solid acid catalyst cathode 105 is sandwiched between the cation exchange membrane 106 and the cathode 104, thereby forming a migration path for the metal cations. This arrangement differs from the direct contact arrangement used in the prior art and is a structure for controlling the deposition position of the metal cations.

[0101] Figure 51 shows the microstructure of the solid acid catalyst cathode 105. The solid acid catalyst cathode 105 has a structure in which the surface of carbon fibers 118 is coated with a solid acid (mainly a polymer containing sulfonic acid groups). The carbon fibers 118 are arranged in a network-like configuration, which provides mechanical strength and electronic conductivity. The solid acid coating uniformly covers the surface of the carbon fibers 118, forming a cation conduction path.

[0102] Figure 52 shows the electrolysis effect in a comparative PEM system. In the comparative PEM system, the cathode side of the diaphragm (Nafion in this case) is alkaline due to the generation of hydroxyl groups (OH-) and other ions due to the electrolysis effect on the cathode side. In this environment, ions such as calcium ions that are mixed with the tap water to be treated and reach the cathode side through the diaphragm are instantly converted to calcium hydroxide. This calcium hydroxide, which is an insulator, accumulates on the surface of the cathode and inhibits electrolysis. This results in the ozone water generator ceasing to function. Because calcium hydroxide adheres strongly to the cathode, it does not peel off when subjected to hydrogen aeration.

[0103] Figure 53 shows the electrolysis process of a PEM system using a solid acid catalyst as the cathode in this embodiment. A fibrous electrode coated with a solid acid catalyst, i.e., the solid acid catalyst cathode 105, is placed so that the space on the cathode side is filled. As a result, the water itself becomes alkaline due to the cathode action, but the space is essentially made more acidic by the countless fixed acid catalysts. This prevents calcium ions from converting to calcium hydroxide. Calcium ions pushed into a normal alkaline environment (outside the range of the solid acid catalyst, i.e., around the SUS cathode 104) by hydrogen gas aeration or the like convert to calcium hydroxide. However, even if calcium hydroxide is formed in this location, the solid acid catalyst cathode 105 continues to function as an electrode, preventing the electrolysis from being hindered.

[0104] FIG. 54 shows a hypothetical situation in which calcium hydroxide is generated even in an environment where the solid acid catalyst cathode 105 of this embodiment is installed. In this embodiment, by using the solid acid catalyst cathode 105 in combination, countless carbon fiber cathodes become the calcium hydroxide generation area. This is because hydroxyl groups are easily generated on the surface of the carbon fiber cathode. Furthermore, the surface area of ​​the cathode increases three-dimensionally, distributing the electrolysis load as a cathode. In other words, it takes a very long time for calcium hydroxide to accumulate in an amount that would interfere with electrolysis. In other words, load distribution and increased capacity are achieved. Furthermore, because of the porous structure, hydrogen aeration provides high discharge efficiency, and the discharge speed is fast relative to the accumulation speed. In other words, high discharge efficiency is achieved. These factors also play a major role in achieving a stable, long-term life.

[0105] Figure 55 shows a hypothetical situation in which calcium hydroxide is produced in a comparative example. The calcium hydroxide production location is a two-dimensional area on the electrolysis surface. The load is concentrated, and accumulation of an amount that interferes with electrolysis occurs relatively quickly.

[0106] The actual effect of cation discharge by the solid acid catalyst cathode will be described with reference to FIGS.

[0107] Figure 56 shows the overall appearance of the assembled electrolytic cell 1. Figure 57 shows an exploded view of each component. Figure 56 shows the exterior of the completed electrolytic cell 1. The electrolytic cell 1 has a compact, cylindrical design and houses the aforementioned components. External connections include electrical wiring and a water inlet / outlet, allowing for easy installation in an actual operating environment. Figure 57 is an exploded view of the electrolytic cell 1, clearly showing the relative positions of the components. From left to right, the following components are arranged: the holder body 110, titanium fiber 109, anode 108, porous cation-exchange membrane layer 107, cation-exchange membrane 106, solid acid catalyst cathode 105, SUS cathode 104, internal pressure spring 103, and holder lid 102. Assembling these components in the appropriate order and with the appropriate pressure achieves highly efficient ozone water generation and metal ion discharge.

[0108] 58 to 63 show actual images of the cation deposition state before and after use of the solid acid catalyst cathode 105.

[0109] Figure 58 shows the surface condition of the cation exchange membrane 106 in a comparative configuration that does not use the solid acid catalyst cathode 105. It can be seen that a large amount of white precipitate P (mainly calcium compounds) has adhered to the membrane surface, which appears to be inhibiting ion conduction. This precipitate P reduces the effective area of ​​the membrane, resulting in a significant drop in electrolysis efficiency.

[0110] 59 shows the surface condition of the cation exchange membrane 106 when the solid acid catalyst cathode 105 according to the embodiment of the present invention is used. The membrane surface is kept clean, and almost no precipitate P is observed. This allows stable electrolysis without impeding ion conduction.

[0111] Figure 60 shows the state of the solid acid catalyst cathode 105 itself, showing both the electrolytic surface (left) and the intermediate layer (right). There is little precipitate P on either surface, which indicates that metal cations are passing through the solid acid catalyst layer and reaching the cathode 104.

[0112] Figures 61 and 62 show the surface of the cathode 104, where metal cation precipitates P can be seen. In Figure 61, precipitates P are formed along a spiral structure, while Figure 62 shows precipitates P concentrated around the punched holes. These indicate that metal cations pass through the solid acid catalyst cathode 105 and reach the cathode 104, where they precipitate as the environment changes from an acidic environment filled with solid acid catalyst to an alkaline environment. Figure 63 shows precipitates P being discharged from the outlet 102a, and it can be seen that the metal cation precipitates P are being efficiently discharged as hydrogen gas is generated. This prevents passivation of the surface of the cathode 104, maintaining stable electrolysis performance over a long period of time.

[0113] The configuration and operation method of a practical system for an ozone water generator according to an embodiment of the present invention will be described with reference to Fig. 64 to Fig. 66. Fig. 64 is a diagram showing a conventional strong acid cleaning system as a comparative example. Fig. 65 is a diagram showing an in-line use configuration of an electrolysis cell 1 according to an embodiment of the present invention. Fig. 66 is a diagram showing a remixing system in an environment where there are restrictions on hydrogen discharge.

[0114] These figures show the differences between the actual operation of an ozone water generator according to an embodiment of the present invention and the prior art. Figure 64 shows a conventional strong acid cleaning system as a comparative example. In conventional PEM electrolytic cells, periodic cleaning with strong acid (hydrochloric acid or nitric acid) was required to remove metal deposits P that accumulated on the cathode. As shown in the figure, peripheral equipment such as tanks, pumps, and piping are required, which increases the system size and introduces risks associated with handling strong acid.

[0115] Figure 65 shows a configuration in which an electrolytic cell 1 according to an embodiment of the present invention is used in-line. The electrolytic cell 1 is directly connected to a pipe 122, enabling continuous production of ozone water. A tube 123 is connected to the outlet 102a of the holder lid 102, allowing efficient discharge of hydrogen gas and mineral precipitates P. The use of a porous cation exchange membrane layer 107 also enhances the cooling effect (water-cooling effect) caused by water flow, suppressing thermal decomposition of ozone O3.

[0116] Figure 66 shows an alternative configuration for environments with restrictions on hydrogen discharge. In this configuration, the discharged hydrogen gas is remixed with the ozone water output side, eliminating the need for hydrogen gas separation and discharge equipment. Although the ozone O3 concentration decreases slightly when hydrogen gas and ozone O3 are mixed, because they are separated at the time of electrolysis, the concentration decrease is more gradual than in conventional hydrogen-mixing cells. This method makes it possible to use the electrolysis cell 1 of the present invention even in environments with restrictions on hydrogen gas discharge equipment.

[0117] A comparative example of a submerged use configuration will be described with reference to Figures 67 and 68. Figure 67 is a diagram showing an electrolysis cell 1 in a submerged use configuration of the comparative example. Figure 68 is a diagram showing the discharge of hydrogen and minerals during submerged use.

[0118] As shown in Figure 67, in the comparative example of immersion use, the electrolytic cell 1 is used by immersing it in a water tank 124. In this configuration, the entire electrolytic cell 1 is placed in the water tank 124, and ozone water is produced.

[0119] As shown in Figure 68, when used for immersion, the electrolytic cell 1 is designed to discharge hydrogen gas (H2) and mineral precipitates P (Ca, etc.) from a large opening at the top, while also dissipating heat. The hydrogen gas diffuses into the water W surrounding the electrolytic cell 1, and the mineral precipitates P settle at the bottom of the container. While this method has few disadvantages for small sprayers, it presents a challenge in large systems, as it makes efficient discharge difficult.

[0120] Other advantages of this embodiment are described below. The holder lid 102 can be made of polyphenylene sulfide resin (hereinafter referred to as "PPS" or "PPS resin"). PPS has a continuous operating temperature of 200°C or higher and is resistant to acids and alkalis, making it suitable for the ozone O3 water generation environment. The PPS resin used in this embodiment is a high-performance engineering plastic characterized by high heat resistance (continuous operating temperature of 200°C or higher) and excellent chemical resistance. PPS has a rigid main chain molecular structure in which benzene rings and sulfur atoms are alternately bonded, providing excellent thermal stability and chemical resistance. In the ozone water generation environment, PPS is exposed to the strong oxidizing effect of ozone O3 and the acidic and alkaline environment caused by the electrolytic reaction, making material selection important. PPS exhibits minimal deformation or degradation even under these harsh conditions, maintaining stable performance over long periods. Furthermore, PPS has moderate hardness and strength, and is highly resistant to internal pressure and mechanical stress. Furthermore, its excellent moldability allows for precise manufacturing of holder lids 102 with complex shapes. These properties make PPS an ideal choice as the holder lid 102 material for the ozone water generator.

[0121] Furthermore, as a measure to improve heat dissipation efficiency, it is preferable that the holder lid 102 be made of a light metal such as aluminum. Furthermore, a heat sink structure improves heat dissipation efficiency. Although this part is likely to come into contact with wiring, it is in contact with the cathode 104, so there is little chance of it corroding. Furthermore, anodizing the part can improve both corrosion resistance and hardness.

[0122] Furthermore, depending on the processing method, aluminum is less expensive than PPS, making it economically preferable. The introduction of an aluminum holder lid 102 significantly improves the thermal management and long-term durability of the ozone water generator. Aluminum has an extremely high thermal conductivity of approximately 237 W / (m·K), approximately 790 times more efficient than PPS, which has a thermal conductivity of approximately 0.3 W / (m·K). This allows for efficient external dissipation of heat generated during the electrolytic reaction, suppressing the thermal decomposition of ozone O3 and maintaining production efficiency. The adoption of a heat sink structure in particular increases the surface area, further enhancing the air-cooling effect. A typical heat sink design is one that employs fin- or pin-shaped protrusions to increase the heat exchange area. Because aluminum has high electrical conductivity, careful consideration is required when designing the contact area with the cathode 104. However, the cathode 104 side is in a reducing environment, so the risk of corrosion is low.

[0123] Furthermore, anodizing (anodic oxidation) forms a dense alumina (Al2O3) layer on the surface, significantly improving corrosion resistance and surface hardness. The anodized layer is typically 5-25 μm thick, and even this thin layer provides sufficient protection. Furthermore, while aluminum has a specific gravity of approximately 2.7, roughly twice that of PPS (1.35), taking into account the difference in thermal conductivity, the volume required to achieve the same heat dissipation performance is significantly less. Furthermore, aluminum has excellent machinability, allowing it to be precisely machined into complex shapes, which often offers advantages in terms of manufacturing costs.

[0124] On the other hand, for the holder parts on the anode 108 side, metal materials cannot be used as they come into contact with the anode 108 and may dissolve. Suitable materials include PPS resin, which has excellent mechanical strength and chemical resistance, and ceramic. The environment on the anode 108 side is particularly harsh, as it is constantly exposed to ozone O3, which has a strong oxidizing effect, and there is also a risk of oxidative decomposition of the material due to the high anode potential. For this reason, metal materials cannot be used, and it is essential to select non-metallic materials with high chemical stability. As mentioned above, PPS resin has excellent heat resistance and chemical resistance, and is stable even in a strong oxidizing environment, making it suitable for the anode side holder parts as well.

[0125] Ceramics are also a promising option, especially fine ceramics such as alumina (Al2O3), zirconia (ZrO2), and silicon nitride (Si2N4), which offer excellent heat resistance, corrosion resistance, and insulation. Ceramics offer superior heat resistance (over 1000°C), surpassing metals and resins, eliminating the risk of thermal deformation. They are also extremely chemically stable and resistant to oxidative decomposition by ozone (O3). They also offer exceptional hardness and resistance to wear and scratches. However, ceramics are brittle and vulnerable to impacts, and precision machining can be costly. In practical design, it is important to compare the properties of PPS resin and ceramic and select the optimal material based on the intended environment, required performance, and cost. Furthermore, because both materials are insulators, a separate conductive component is required for electrical connection to the anode 108.

[0126] With these configurations, the ozone water generator of this embodiment achieves high efficiency and long-term stable operation that could not be achieved with conventional technology. In particular, the improvement of electrolysis efficiency by the porous cation exchange membrane layer 107 and the continuous discharge of cations by the solid acid catalyst cathode 105 significantly reduce the frequency of maintenance, making it possible to provide a practical ozone water generation system.

[0127] The overall advantages of the ozone water generator of this embodiment are realized by a combination of the following technological innovations. First, the introduction of a porous cation exchange membrane layer 107 significantly improves electrolysis efficiency compared to conventional smooth membrane structures. This layer forms porous water channels 112, improving the efficiency of water (W) supply and ozone (O3) transport. It also creates numerous three-interface 126 (contact points between the electrode, electrolyte, and water (W)), increasing the number of active sites for the electrolysis reaction. Second, the solid acid catalyst cathode 105 continuously discharges metal ions, eliminating the need for periodic strong acid cleaning, which was previously required, enabling long-term, maintenance-free operation. This feature enables stable operation even when using ordinary tap water containing hardness components as a raw material, significantly enhancing its practicality. Third, optimal material selection and structural design improve thermal management and durability. The design incorporates intricate details, such as the use of PPS resin, aluminum, and ceramic in the right places, efficient power distribution and heat management using titanium fiber 109, and optimization of the porous cation exchange membrane layer 107 by taking advantage of the characteristics of various substrates 118.

[0128] By integrating these technological innovations, the ozone water generator of this embodiment has realized a practical system that combines high efficiency (power saving), long-term stability (maintenance-free), and compactness (simple structure). This will significantly expand the application fields of ozone water, which have previously been limited due to technical and economic constraints, and is expected to be used in various industrial fields such as water treatment, sterilization / disinfection, agriculture, and food processing.

[0129] Although one embodiment of the present invention has been described above, the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the scope that can achieve the object of the present invention are included in the present invention.

[0130] The ozone water generator includes a cathode 104, a cation exchange membrane 106 that allows cations to pass through, an anode 108, and a porous cation exchange membrane layer 107 that is disposed between the cation exchange membrane 106 and the anode 108 and has water passages 112 with a porous structure. This forms a large number of electrolysis points (three interfaces 126) where the anode 108 and water W come into contact and the cathode 104 is close, making it possible to achieve high electrolysis efficiency that could not be achieved with conventional smooth membrane structures.

[0131] Furthermore, in the ozone water generating apparatus, the anode 108 can be an oxidation-reduction resistant electrode, for example, a boron-doped diamond electrode, platinum, glass carbon, lead oxide, or conductive tin oxide. As a result, the structure is not corroded during the anodic reaction, and all of the energy that would otherwise corrode the metal anode is used to decompose water W, enabling the generation of high-concentration ozone O3.

[0132] Furthermore, in the ozone water generating apparatus, the anode 108 may have a plurality of slit structures 108a. As a result, the water W that has passed through the gaps in the anode 108 reaches the electrolytic surface 125 of the cation exchange membrane 106, and the ozone O3 passes through the slit structure 108a, so that the ozone O3 is efficiently added to the water flow.

[0133] Furthermore, in the ozone water generating apparatus, the porous cation exchange membrane layer 107 can also be formed by coating a fibrous porous substance, such as carbon fiber, with a cation exchange membrane material and then removing the porous substance, for example, by electrolysis. As a result, the carbon fibers are removed in parallel with the process of generating ozone O3 water by electrolysis, and water W flows through the porous structure or capillary structure, improving the electrolysis efficiency and removing carbon incidentally during the electrolysis process without the need for a prior process of removing carbon fibers.

[0134] Furthermore, the ozone water generating apparatus further includes a cathode layer containing a solid acid catalyst between the cathode 104 and the cation exchange membrane 106, and the cathode layer containing the solid acid catalyst can also have the function of moving metal ions in the water W to the cathode 104 and depositing them. By doing so, the location where the cations receive the electrons e is located at a position other than on the cation exchange membrane 106, and the non-conductor is continuously discharged as it is deposited, making it possible to perform stable electrolysis over a long period of time.

[0135] Furthermore, the ozone water generating device may further include a conductive layer made of a porous material, such as titanium fiber 109, between the anode 108 and the porous cation exchange membrane layer 107. This allows the contact to be located over the entire anode 108 while still having a certain degree of elasticity, resulting in a more stable contact, and furthermore, since the structure is permeable to ozone O3 and water W, it is possible to take advantage of the advantages of the slit structure 108a of the anode 108 while also reducing thermal damage.

[0136] Furthermore, in the ozone water generating apparatus, the cation exchange membrane 106 and the porous cation exchange membrane layer 107 may contain at least one selected from the group consisting of a polar long-chain functional group, such as perfluorosulfonic acid polymer, sulfonated polystyrene, sulfonated polyether ether ketone, sulfonated polyphenylene oxide, sulfonated polysulfone, sulfonated polyimide, sulfonated polybenzimidazole, sulfonated polyethersulfone, carboxylated polybenzimidazole, phosphated polyvinyl alcohol, graft copolymers containing sulfonic acid groups, and block copolymers containing sulfonic acid groups. This allows the electrolyte membrane to function as an electrolyte membrane with proton conductivity, ion exchange, and electrical conductivity, and can maintain stable performance over a long period of time even in high-temperature, high-pressure electrolysis environments.

[0137] Furthermore, in the ozone water generating apparatus, a plurality of the anodes 108 can be arranged in a ring shape. This allows the heat-generating surfaces to be separated from one another, resulting in an electrode configuration with high heat dissipation efficiency. The distance between each electrode is maintained, improving heat dissipation efficiency. It also allows electrodes of any surface area to be combined while maintaining the benefits of the microstructure. [Explanation of symbols]

[0138] 1: Electrolytic cell, 101: Waterproof / power supply electrode for energization, 102: Holder lid, 102a: Outlet, 103: Internal pressure spring, 104: SUS cathode, 104a: Punch structure, 105: Solid acid catalyst cathode, 106: Cation exchange membrane (Nafion membrane), 107: Porous cation exchange membrane layer (Nafion carbon), 108: Anode, 108a: Slit structure, 109: Titanium fiber, 110: Holder body, 110a: Water inlet / outlet, 111: Waterproof / power supply electrode for energization Pole, 112: Water passage, 113: Flow path structure, 114: Double annular water passage, 115: Packing, 116: Master, 117: Niobium plate, 118: Base material, 119: Carbon base paper, 120: Kiln, 121: PP plate, 122: Piping, 123: Tube, 124: Water tank, 125: Electrolysis surface, 126: Three interfaces, 127: Cavity, 128: Water passage space, W: Water, O3: Ozone, H: Hydrogen ion, e: Electron, P: Precipitate, R: Resin, L: Liquid Nafion, S: Solvent, B: Bacteria

Claims

1. An apparatus for generating ozone water by electrolysis, A cathode; a cation exchange membrane that allows cations to pass through; an anode; a porous cation exchange membrane layer disposed between the cation exchange membrane and the anode and having water passages with a porous structure; An ozone water generating device comprising:

2. The anode is a redox-resistant electrode. The ozone water generating apparatus according to claim 1.

3. The anode has a plurality of slit structures.

3. The ozone water generating apparatus according to claim 1 or 2.

4. The porous cation exchange membrane layer is formed by coating a fibrous porous substance with a cation exchange membrane material and then removing the porous substance. The ozone water generating device according to claim 1.

5. a cathode layer containing a solid acid catalyst between the cathode and the cation exchange membrane; 2. The ozone water generating apparatus according to claim 1, wherein the cathode layer containing the solid acid catalyst has a function of moving metal ions in water to the cathode and depositing them.

6. a porous conductive layer is further provided between the anode and the porous cation exchange membrane layer; The ozone water generating device according to claim 1.

7. the cation exchange membrane and the porous cation exchange membrane layer have a polar long-chain functional group; The ozone water generating device according to claim 1.

8. A plurality of the anodes are arranged in a ring shape. The ozone water generating device according to claim 1.

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