Electrolytic cell and method for manufacturing the same

Abstract

This disclosure relates to an electrolytic cell comprising a porous transport layer including at least one metal support layer and at least one macroporous layer containing titanium particles deposited on the at least one support layer, wherein the titanium particles are at least partially covered with at least one conductive titanium oxide surface layer.

Description

[Technical Field]

[0001] This disclosure relates to an electrolytic cell comprising a porous transport layer including at least one metal support layer and at least one macroporous layer containing titanium particles deposited on the at least one support layer, wherein the titanium particles are at least partially covered with at least one conductive titanium oxide surface layer. [Background technology]

[0002] Electrolytic cells convert water into oxygen and hydrogen, and are most efficient when operated at high current density and low cell voltage. Currently, various types of electrolytic cells exist on the market. However, one challenge with these cells is that high current density cannot be achieved at low cell voltages.

[0003] To obtain high current density at low cell voltage, it has been shown that careful selection of the components constituting the electrolytic cell is crucial. One of the most important components is the porous transport layer, which greatly affects the ohmic cell resistance and, consequently, the cell voltage. The ohmic cell resistance is determined, in particular, by the contact resistance between the porous transport layer and the catalyst layer.

[0004] The present invention aims to solve the above problems by providing an electrolytic cell equipped with a new type of porous transport layer, which is easier to manufacture and provides a desired ohmic cell resistance, i.e., a low cell voltage at high current density. [Overview of the project]

[0005] Therefore, this disclosure states that the electrolytic cell is Anode section, Anode plate; A selectively chosen anode flow field; Conductive anode porous transport layer; and Anode catalyst layer an anode section including, membrane and Cathode section, Cathode plate; Selective cathode flow field; Conductive cathode porous transport layer; and Cathode catalyst layer Cathode section including Regarding electrolytic cells, including, The membrane separates the cathode compartment from the anode compartment; The anode and cathode compartments are configured to be supplied with fluid; At least one of the conductive anode porous transport layer or the conductive cathode porous transport layer is At least one metal support layer in the form of a three-dimensional open porous structure; and At least one macroporous layer having the form of at least one metal support layer, the at least one macroporous layer containing titanium particles It consists of, Titanium particles, TiO x and / or at least partially covered with at least one conductive titanium oxide surface layer containing Ti3O, where x is 0.7 to 1.3 It is characterized by the following:

[0006] The electrolytic cell of the present invention will have low ohmic cell resistance and good water electrolysis efficiency, as it has been found that at least one titanium oxide surface layer is conductive and electrons can pass through at least one macroporous layer. Although not bound by any theory, this conductivity is thought to be due to the composition of the titanium oxide surface layer.

[0007] The present invention also relates to a manufacturing process for an electrolytic cell as defined above or below, the process comprising the following steps for manufacturing a conductive anode porous transport layer or a conductive cathode porous transport layer: - To provide at least one metal support layer. - To provide titanium particles - exposing titanium particles to a high-velocity atmospheric spraying process, thereby forming at least one macroporous layer while depositing the titanium particles on at least one metal support layer comprising the high-velocity atmospheric spraying process is carried out at a temperature below the melting point of the titanium particles, and the atmospheric spraying process has an atmosphere with an O2:CH4 ratio of 0.3 - 0.7:1. This process will result in the formation of at least one titanium suboxide surface layer defined above or below.

[0008] Furthermore, the present disclosure relates to an electrolytic cell stack comprising at least one electrolytic cell as defined above or below. The electrolytic cell stack can be either a proton exchange membrane (PEM) water electrolysis device or an anion exchange membrane (AEM) water electrolysis device.

[0009] The present invention is further illustrated by the following non-limiting drawings.

Brief Description of the Drawings

[0010] [Figure 1] It is a schematic diagram of a cell of a PEM water electrolysis device. [Figure 2] It is a schematic diagram of a conductive porous transport layer as defined above or below. [Figure 3A-B] SEM micrograph of the cross-section of a reference sample with a titanium particle macroporous layer deposited by high-velocity oxygenated air-fuel (HVOAF) spraying with an O2:CH4 ratio of 1.05:1; different magnifications are defined by the scale bars of the respective micrographs. [Figure 3C-D] SEM micrograph of the cross-section of a conductive porous transport layer deposited by HVOAF spraying with an O2:CH4 ratio of 0.55 - 1 in accordance with the present disclosure, as defined above or below in accordance with the present disclosure; different magnifications are defined by the scale bars of the respective micrographs. [Figure 3E-F]SEM micrograph of the cross-section of a reference sample on which a titanium particle macroporous layer is deposited by a high-velocity oxygen-air fuel (HVOAF) spray with an O2:CH4 ratio of 0:97:1; different magnifications are defined by the scale bars of the respective micrographs. [Figure 3G-H] SEM micrograph of the cross-section of a conductive porous transport layer deposited by an HVOAF spray with an O2:CH4 ratio of 0.65 to 1, according to the present disclosure, as defined above or below according to the present disclosure; different magnifications are defined by the scale bars of the respective micrographs. [Figure 4] A and B are SEM micrographs of the polished cross-section of a spherical titanium particle macroporous layer at different magnifications defined by the scale bars of the respective micrographs. [Figure 5] X-ray diffraction pattern of the macroporous layer (solid line) and the spherical powder (dashed line) before exposure to HVOAF. [Figure 6] Graph showing the polarization curves and the iR-free polarization curves (dashed lines) of different PEM water electrolysis single cells of Example 2. [Figure 7] A - C are SEM micrographs of the polished cross-section of a titanium non-spherical particle macroporous layer. Figure 7A shows the results of a high O2:CH4 ratio, and Figures 7B and 7C show the results of a low O2:CH4 ratio. [Figure 8] A and B are SEM micrographs at low (A) and high (B) magnifications of the polished cross-section of non-spherical Ti powder deposited on a MeliDiff 1500 316L substrate. The scale bars in the micrographs indicate the size. [Figure 9] Graph showing the polarization curves and the iR-free polarization curves (dashed lines) of different PEM water electrolysis single cells. [Figure 10] Graph showing the polarization curves and the iR-free polarization curves (dashed lines) of different PEM water electrolysis single cells of Example 4.

Mode for Carrying Out the Invention

[0011] The present disclosure is such that the electrolytic cell 1 is an anode compartment 2, Anode plate 3; Optionally, an anode flow field 4; Conductive anode porous transport layer 5; and Anode catalyst layer 6 Anode section 2 and Membrane 7 and, Cathode section 8, Cathode plate 9; Optionally, cathode flow field 10; Conductive cathode porous transport layer 11; and Cathode catalyst layer 12 Cathode section 8 and Regarding the electrolytic cell 1, which is equipped with the following, The membrane 7 separates the cathode compartment 8 from the anode compartment 2; Anode section 2 and cathode section 8 are configured to be supplied with fluid; At least one of the conductive anode porous transport layer 5 or the conductive cathode porous transport layer 11 is At least one metal support layer I in the form of a three-dimensional open porous structure; and At least one macroporous layer II deposited on at least one metal support layer I, the at least one macroporous layer II containing titanium particles III It consists of, Titanium particles III, TiO x and / or at least partially covered with at least one conductive titanium oxide surface layer IV containing Ti3O, where x is 0.7 to 1.3 It is characterized by the following:

[0012] According to this disclosure, at least one metal support layer I has the form of a three-dimensional open porous structure, and these open pores are interconnected, which will ensure good mass transport properties. Furthermore, in this disclosure, the term "macropore" means a pore larger than 50 nanometers.

[0013] Surprisingly, it was found that at least one macroporous layer II allows electrons to pass through even without complete metallic contact between individual titanium particles III. While not bound by any theory, it is thought that the conductivity of the titanium oxide surface layer IV facilitates electron passage. Furthermore, at least one macroporous layer II will increase the total contact area between the porous transport layers 5, 11 and the catalyst layers 6, 12. The increased contact area will improve the distribution of contact points and reduce the contact resistance between the porous transport layers 5, 11 and the catalyst layers 6, 12, thereby reducing the ohmic resistance within the electrolytic cell 1. When the porous transport layer 5 of the present invention is used in the anode compartment 2, the porous structure will increase the transport of water to the anode catalyst layer 6 due to capillary forces. Furthermore, the porous transport layer 5 will simultaneously prevent the formation of large oxygen bubbles that would hinder further water transport to the anode catalyst layer 6. All of these effects will reduce mass transport losses and thereby improve the efficiency of the electrolytic cell 1.

[0014] According to one embodiment, the conductive anode porous transport layer 5 may be exactly the same as the conductive cathode porous transport layer 11.

[0015] According to the embodiment, the conductive anode porous transport layer 6 may differ from the conductive cathode porous transport layer 11. Examples of differences, though not limited to, include: being composed of different components; being composed of different materials; having different particle sizes for the titanium particles; having different pore sizes for the macroporous layer; and having different structures or being composed of different materials for the metal support layer.

[0016] According to the embodiment, the titanium particles may be spherical or non-spherical.

[0017] Other suitable porous transport layers used when the anode porous transport layer differs from the cathode porous transport layer include, but are not limited to, carbon porous structures (cathode) and metal fiber felt, such as stainless steel fiber felt (cathode) or titanium fiber felt (anode).

[0018] According to the embodiment, the anode porous transport layer 5 is a porous transport layer in which titanium particles are partially covered with titanium oxide, as defined above or below, and the cathode porous transport layer 11 is a carbon porous structure or stainless steel fiber felt.

[0019] According to the embodiment, the cathode porous transport layer 11 is a porous transport layer in which titanium particles are partially covered with titanium oxide, as defined above or below, and the anode porous transport layer 5 is titanium fiber felt.

[0020] According to the embodiment, at least one conductive titanium oxide surface layer IV contains more than 50 volume% TiO x It contains titanium dioxide IV. This improves conductivity and makes it even more certain that electrons can pass through the porous transport layers 5 and 11. As shown in Figure 2, which shows schematic diagrams of the porous transport layers 5 and 11, titanium dioxide IV can be present as a coating covering part or all of the surface of the titanium particles III, and as junctions between the titanium particles III. According to the embodiment, at least one conductive titanium dioxide surface layer IV has a thickness ranging from 100 nm to 5 μm.

[0021] According to the embodiment, the pore size of at least one macroporous layer II is in the range of 1 to 100 μm in order to ensure sufficient capillary force.

[0022] According to the embodiment, the porosity of at least one macroporous layer II is in the range of 10 to 70 volume percent. This will ensure that fluids such as water, oxygen, and hydrogen are transported through the layer.

[0023] According to the embodiment, at least one macroporous layer II has a thickness in the range of 10 to 500 μm. This will ensure sufficient corrosion protection as needed. The thickness of the macroporous layer II may correlate with the desired pore size and / or particle size of the titanium particles II.

[0024] According to the embodiment, there may be multiple macroporous layers, and these macroporous layers may be the same or different. In this specification, "different" means, but is not limited to, being composed of different particles (meaning the particles may be composed of different materials), having different particle sizes, having different structures, etc. According to the embodiment, different particle sizes may exist in the same macroporous layer II.

[0025] According to one embodiment, the number of macroporous layer II can be 1 to 20, for example 1 to 10, or for example 1 to 5.

[0026] According to the embodiment, at least one metal support layer I may be selected from the group consisting of wire mesh, expanded metal, perforated metal, or a combination thereof. According to the embodiment, the perforated metal may be a perforated metal sheet obtained by laser cutting or other cutting methods.

[0027] According to the embodiment, the pore size of the pores in at least one metal support layer I is in the range of 5 μm to 5 mm. The at least one metal support layer may have the same pore size throughout the entire layer, or it may have different pore sizes throughout the entire layer.

[0028] According to the embodiment, the number of metal support layers may be in the range of 1 to 15, for example 1 to 10, for example 2 to 8, for example 3 to 7.

[0029] In the electrolytic cell 1, all the components shown in Figure 1 are sandwiched between two plates 3 and 9, also known as electrodes. These plates 3 and 9 ensure the stability of the cell 1. These electrodes are made of a metallic material and may or may not be formed to include a flow field structure within the plates themselves.

[0030] The flow fields 4 and 10 are optional and can be included, for example, when plates 3 and 9 are not formed, i.e., when a flat structure is present. The flow fields will facilitate the introduction of starting materials and the removal of products.

[0031] According to the embodiment, the fluid of the electrolytic cell 1 can be selected from water, alkali hydroxide solution, or aqueous gas. Examples of alkali hydroxide solutions include NaOH(l) or KOH(l) aqueous gas. The aqueous gas, i.e., the humidifying gas, may be humidified air. According to the embodiment, the fluid of the anode compartment 2 may be different from the fluid of the cathode compartment 8.

[0032] This disclosure also relates to a manufacturing process for the electrolytic cell 1 as defined above or below, wherein the process comprises the following steps for manufacturing a conductive anode porous transport layer 5 or a conductive cathode porous transport layer 11: - To provide at least one metal support layer I; - To provide titanium particles III; - Exposure of titanium particles III to a high-speed atmospheric spraying process, thereby forming at least one macroporous layer II while depositing titanium particles III on at least one metal support layer II. Including, here, The high-speed atmospheric atomization process is carried out in a process atmosphere having an O2:CH4 ratio of 0.3 to 0.7:1 at a temperature below the melting point of titanium particles III.

[0033] This process will result in the formation of the desired titanium IV oxide. Furthermore, the porous transport layers 5 and 11 obtained by this process will have electronic conductivity through the deposited layer II, even though complete metallic contact between individual titanium particles does not occur due to the formation of titanium IV oxide. Moreover, the titanium particles III will form macropores in at least one macroporous layer II. The high-speed atmospheric spraying process is carried out until the desired thickness and amount of titanium IV oxide is formed and a macroporous layer II of the desired thickness is obtained.

[0034] This disclosure is further illustrated in the following non-limiting embodiments. [Examples]

[0035] Example 1 Argon-sprayed spherical titanium powder grade 1 with particle size D15-45 μm was used. The metal support layer used was 316L stainless steel plate for samples 1 to 4, and MeliDiff 1500 316L stainless steel (expanded metal mesh laminate) for sample 5.

[0036] Titanium particles were sprayed onto a support layer using a high-speed oxygen-air fuel (HVOAF) process. Multiple spraying cycles were performed to obtain the desired structure.

[0037] The gas mixture used consisted of air, nitrogen, CH4 (natural gas), and O2. Although air also contains nitrogen and oxygen, additional amounts of these gases were added to the gas mixture.

[0038] The gas mixture always contained the same amounts of air and nitrogen, at 1500 slpm (standard liters / minute) and 80 slpm (standard liters / minute), respectively. By changing their ratio, the content of O2 and CH4 in the gas mixture was altered (see Table 1). TIFF2026516287000002.tif17170

[0039] As can be seen from Figures 3A and 3B and Figures 3E and 3F, a high O2:CH4 ratio will result in a fine microstructure so dense that mass transport of water and oxygen within the electrolytic cell using Sample 2 and Sample 1 is impossible. Furthermore, as can be seen from Figures 3C and 3D and Figures 3G and 3H, a low O2:CH4 ratio will result in the desired macroporous structure (Sample 3 and Sample 4), thereby obtaining an electrolytic cell with the desired properties. Sample 3 had a macroporous layer with a thickness in the range of 150 to 250 μm.

[0040] The polished cross-section of sample 5 was investigated by SEM / EDS (Surface-Electrical Electron Microscopy / Energy-Dispersive Spectroscopy) using a Zeiss Sigma VP FEG-SEM instrument equipped with an Oxford EDS detector. Micrographs obtained at 250x and 4000x magnification using a 10kV accelerating voltage and backscatter detector are shown in Figures 4A and 4B. In Figure 4B, the bright contrast region is associated with titanium powder particles, while the dark contrast region at the particle interface indicates the oxygen-rich titanium phase. The thickness range of the titanium oxide phase was measured to be 100nm to 5μm in the micrographs.

[0041] Co K in GI mode (1° oblique incidence) α The phase of the macroporous layer of sample 5 was investigated using XRD (X-ray diffraction) with a Bruker D8 Advance diffractometer equipped with a source, Goebel mirror, and LynxEye XE Si strip detector with an equatorial solar slit on the front. The diffraction pattern obtained in Figure 5 shows titanium dioxide (TiO2). x The presence of TiO2 and Ti3O was observed, but stoichiometric TiO2 was not present. The diffraction pattern of titanium particles before the start of the process showed the presence of only the titanium phase. Therefore, the formed titanium monoxide originated from the HVOAF process. TiO2 at oxygen-rich interfaces between titanium particles x The presence of Ti3O was also confirmed by EBSD (electron backscatter diffraction).

[0042] Example 2 The effects of different anodic porous transport layers in a PEM water electrolysis (PEMWE) single cell were investigated. The results are shown in Figure 6. The cells tested are shown in Table 2. For different components and their positions within the cells, refer to Figure 1. The anodic porous transport layer of Cell C was Sample 5 of Example 1. TIFF2026516287000003.tif58170

[0043] Figure 6 shows the polarization curves of Cells A, B, and C. In Figure 6, the term "without iR" means the value obtained by subtracting the increase in ohmic voltage (voltage = current [i] × ohmic resistance [R]); this parameter is used to show the mass transfer behavior of the cell.

[0044] From these measurements, it is shown that the polarization curve of Cell A has a very high potential even at current densities below 0.25 A cm -2 This is thought to be due to the corrosion of MeliDiff 1500 316L caused by the high potential at the APTL(5) / ACL(6) interface. This means that in Cell A, the PTL made of stainless steel is not stable and the corrosion is rapid, making the operation of the cell impossible. In Cell B, the PTL(5) on the anode side is composed of MeliDiff 1500 Ti, and titanium is a material that shows corrosion stability even at high potentials at the APTL(5) / ACL(6) interface. Therefore, a stable polarization curve up to 2 A cm -2 was obtained at a cell voltage of 2.2V. However, the without iR curve of Cell B still shows a considerable slope. This slope is due to unfavorable mass transfer characteristics. This slope is also the reason for the higher cell voltage compared to Cell C.

[0045] Furthermore, Figure 6 shows that Cell C shows a lower cell voltage (1.965 V vs 2.2 V) than Cell B at 2 A cm -2 This shows that the without iR curve of Cell C is due to excellent mass transfer mainly obtained by the presence of the macroporous layer. Furthermore, compared to the without iR curve of Cell B, which shows a considerable slope, at 0.5 A cm-2 This is evident from the fact that the iR-free curve has no slope at current densities exceeding a certain threshold. On the other hand, the iR-free curve for cell B shows a considerable slope.

[0046] Furthermore, the ohm cell resistance of cells B and C is HFR (1A cm). -2 (High-frequency resistance at) 200 mΩ cm 2 and 189 mΩ cm 2 It was determined that this is the case. This indicates that the ohmic cell resistance of cell C is lower compared to cell B. Without being bound by theory, since the cells have the same components except for APTL(5), this result is thought to be due to the macroporous layer. Therefore, selecting appropriate components in electrolytic cells is extremely important.

[0047] Finally, comparing the polarization curves of cell A and cell C, it is shown that the stainless steel component (MeliDiff 1500 316L) is stabilized by the presence of a macroporous layer of spherical titanium particles covered with at least one conductive titanium oxide surface layer, and does not corrode despite the high potential at the APTL(5) / ACL(6) interface. This is at least 2A cm -2 It has been shown that a stable polarization curve can be recorded up to that point. Without being bound by any theory, the low ohmcell resistance of the samples prepared as described in samples 4 and 5 suggests that this porous transport layer can also be used on the cathode side. This is supported by the presence of a Ti suboxide layer that can act as an effective barrier layer against hydrogen absorption to the particles.

[0048] Therefore, it was found that by carefully selecting the components of the electrolytic cell, this electrolytic cell would have low ohmic losses.

[0049] Example 3 Commercially available non-spherical pure titanium powder with less than 5000 ppm of oxygen and a particle size distribution of 0 < powder size < 45 μm was used. The metal support layer used was 316L stainless steel plate for samples 6 to 8, and MeliDiff 1500 316L stainless steel (expanded metal mesh laminate) for sample 9.

[0050] Titanium particles were sprayed onto a support layer using a high-speed oxygen-air fuel (HVOAF) process. Multiple spraying cycles were performed to obtain the desired structure.

[0051] The gas mixture used consisted of air, nitrogen, CH4 (natural gas), and O2. Although air also contains nitrogen and oxygen, additional amounts of these gases were added to the gas mixture.

[0052] The gas mixture always contained the same amounts of air and nitrogen, at 1500 slpm (standard liters / minute) and 80 slpm (standard liters / minute), respectively. By changing their ratio, the content of O2 and CH4 in the gas mixture was altered (see Table 3). TIFF2026516287000004.tif17170

[0053] As can be seen from Figure 7A, the high O2:CH4 ratio used in sample 6 will result in a fine microstructure so dense that mass transport of water and oxygen within the electrolytic cell is impossible. Furthermore, as can be seen from Figures 7B and 7C, a low O2:CH4 ratio will result in the desired macroporous structure (samples 7 and 8), thereby yielding an electrolytic cell with the desired properties. Samples 6, 7, and 8 had macroporous layers with thicknesses ranging from 100 to 150 μm.

[0054] The polished cross-section of sample 9 was investigated by SEM / EDS (Scanning Electron Microscope / Energy Dispersive Spectroscopy) using a Zeiss Sigma VP FEG-SEM instrument equipped with an Oxford EDS detector. Micrographs obtained at 200x and 2000x magnification using a 10kV accelerating voltage and backscatter detector are shown in Figures 8A and 8B. Similar to sample 5 in Figure 4B, the dark contrast regions in Figures 8A and 8B located at the particle interface indicate an oxygen-rich titanium phase. The thickness range of the titanium oxide phase was measured to be 200 nm to 6 μm in the micrographs.

[0055] Co K in GI mode (1° oblique incidence) α The phase of the macroporous layer of sample 9 was investigated using XRD (X-ray diffraction) with a Bruker D8 Advance diffractometer equipped with a source, Goebel mirror, and LynxEye XE Si strip detector with an equatorial solar slit on the front. The diffraction pattern obtained in Figure 9 shows titanium dioxide (TiO2). x The presence of TiO2 and Ti3O was observed, but stoichiometric TiO2 was not present. The diffraction pattern of titanium particles before the start of the process showed the presence of only the titanium phase. Therefore, the formed titanium monoxide originated from the HVOAF process. TiO2 at oxygen-rich interfaces between titanium particles x The presence of Ti3O was also confirmed by EBSD (electron backscatter diffraction).

[0056] Example 4 The performance of an anode porous transport layer coated with non-spherical titanium particles in a PEM water electrolysis (PEMWE) single cell was investigated. The results are shown in Figure 10. The cells tested are shown in Table 4. For different components and their positions within the cells, please refer to Figure 1. The anode porous transport layer in cell D was sample 9 from Example 3. TIFF2026516287000005.tif61170

[0057] Figure 10 shows the polarization curve of cell D. In Figure 10, the term "no iR" refers to the value obtained by subtracting the increase in ohmic voltage (voltage = current [i] × ohmic resistance [R]); this parameter is used to describe the mass transfer behavior of the cell.

[0058] Figure 10 shows that cell D is A cm -2 This indicates that it exhibits a cell voltage of 1.920V, which is lower than the cell voltage of cell C in Example 2. Furthermore, the ohmic cell resistance of cell D is also lower than the ohmic cell resistance of cell C in Example 2, with an HFR (1A cm). -2 (High-frequency resistance at) 166 mΩ cm 2 It was determined that this is the case. Although not bound by any theory, this result is thought to be due to the large surface area of ​​the non-spherical titanium powder particles in cell D. This is because, with the exception of APTL(5) in cell D, the cells have the same constituent elements.

[0059] at least 2A cm -2 The stable polarization curves up to 0 indicate that the stainless steel component (MeliDiff 1500 316L) is stabilized by the presence of a macroporous layer of non-spherical titanium particles covered with at least one conductive titanium oxide surface layer, and does not corrode despite the high potential at the APTL(5) / ACL(6) interface. Without being bound by any theory, the low ohmcell resistance of the samples prepared as described in samples 4 and 5 suggests that this porous transport layer can also be used on the cathode side. This is supported by the presence of the Ti oxide layer, which can act as an effective barrier layer against hydrogen absorption to the particles.

[0060] Therefore, it was found that by carefully selecting the components of the electrolytic cell, this electrolytic cell would have low ohmic losses.

Claims

1. Electrolytic cell (1), Anode plate (3); Optionally, an anode flow field (4); Conductive anode porous transport layer (5); and Anode catalyst layer (6) Anode section (2) including, The membrane (7) and Cathode plate (9); Optionally, a cathode flow field (10); Conductive cathode porous transport layer (11); and Cathode catalyst layer (12) Cathode section (8) including and Equipped with, The film (7) separates the cathode section (8) from the anode section (2); The anode section (2) and the cathode section (8) are configured to be supplied with fluid; At least one of the conductive anode porous transport layer (5) or the conductive cathode porous transport layer (11) is At least one metal support layer (I) having the form of a three-dimensional open porous structure; and At least one macroporous layer (II) deposited on the at least one metal support layer (I), the at least one macroporous layer (II) containing titanium particles (III); It consists of, The aforementioned titanium particles (III) are TiO ｘ and / or Ti ３ It is at least partially covered with at least one conductive titanium oxide surface layer (IV) containing O, and x is between 0.7 and 1.

3. An electrolytic cell (1) characterized by the following.

2. The electrolytic cell (1) according to claim 1, wherein the fluid is selected from water, an alkaline hydroxide solution, or a water gas.

3. The electrolytic cell (1) according to claim 2, wherein the fluid in the anode compartment (2) is different from the fluid in the cathode compartment (8).

4. The electrolytic cell (1) according to any one of claims 1 to 3, wherein the conductive anode porous transport layer (5) is the same as the conductive cathode porous transport layer (11).

5. The electrolytic cell (1) according to any one of claims 1 to 3, wherein the conductive anode porous transport layer (5) is different from the conductive cathode porous transport layer (11).

6. The conductive titanium oxide surface layer (IV) contains more than 50 volume% TiO ｘ An electrolytic cell (1) according to any one of claims 1 to 5, having a content.

7. The electrolytic cell (1) according to any one of claims 1 to 6, wherein the at least one conductive titanium oxide surface layer (IV) has a thickness in the range of 100 nm to 5 μm.

8. The electrolytic cell (1) according to any one of claims 1 to 7, wherein the pore size of the at least one macroporous layer (II) is in the range of 1 to 100 μm.

9. The electrolytic cell (1) according to any one of claims 1 to 8, wherein the porosity of at least one macroporous layer (II) is in the range of 10 to 70 volume percent.

10. The electrolytic cell (1) according to any one of claims 1 to 9, wherein the at least one macroporous layer (II) has a thickness in the range of 10 to 500 μm.

11. The electrolytic cell (1) according to any one of claims 1 to 10, wherein the at least one metal support layer (I) is selected from the group consisting of wire mesh, expanded metal, perforated metal, or a combination thereof.

12. The electrolytic cell (1) according to any one of claims 1 to 11, wherein the pore size of the at least one metal support layer (I) is in the range of 5 μm to 5 mm.

13. An electrolytic cell stack comprising at least one electrolytic cell (1) according to any one of claims 1 to 12.

14. The electrolytic cell stack according to claim 13, wherein the electrolytic cell stack is a proton exchange membrane water electrolysis device or an anion exchange membrane water electrolysis device.

15. A method for manufacturing an electrolytic cell (1) according to any one of claims 1 to 13, wherein the method for manufacturing the conductive anode porous transport layer (5) or the conductive cathode porous transport layer (11) is - A step of providing at least one metal support layer (I); - Steps to provide titanium particles (III); - A step of exposing the titanium particles (III) to a high-speed atmospheric spraying process, thereby forming the at least one macroporous layer (II) while depositing the titanium particles on the at least one metal support layer (I). Includes, The high-speed atmospheric spraying process is carried out at a temperature below the melting point of the titanium particles (III), and the process atmosphere is O2 in a ratio of 0.3 to 0.7.

1. ２ :CH ４ Having a ratio, method.

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