ELECTROCHEMICAL PUMP
20190368512 ยท 2019-12-05
Inventors
Cpc classification
F04F9/02
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
C25B9/23
CHEMISTRY; METALLURGY
F04B37/18
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
International classification
Abstract
In an electrochemical hydrogen pump, an anode separator, an anode diffusion layer, an electrolyte membrane, a cathode diffusion layer and a cathode separator are laminated sequentially, in which the anode separator has a first recess portion that accommodates the anode diffusion layer, and a bottom surface of the first recess portion is a bowl-shaped curved surface having a protruding central portion; the cathode separator has a second recess portion that accommodates the cathode diffusion layer, and a bottom surface of the second recess portion is a bowl-shaped curved surface having a recessed central portion.
Claims
1. An electrochemical pump comprising: an anode separator, an anode diffusion layer, an electrolyte membrane, a cathode diffusion layer, and a cathode separator laminated sequentially, wherein the anode separator has a first recess portion that accommodates the anode diffusion layer, and a bottom surface of the first recess portion is a bowl-shaped curved surface having a protruding central portion, and wherein the cathode separator has a second recess portion that accommodates the cathode diffusion layer, and a bottom surface of the second recess portion is a bowl-shaped curved surface having a recessed central portion.
2. The electrochemical pump according to claim 1, wherein the first recess portion has a flow path groove through which gas flows, and wherein the second recess portion has a flow path groove through which gas flows.
3. The electrochemical pump according to claim 1, wherein the anode diffusion layer is disposed in the first recess portion in a pressed state, and wherein the cathode diffusion layer is disposed in the second recess portion in a pressed state.
4. The electrochemical pump according to claim 1, wherein a central portion of the anode diffusion layer protrudes in a bowl shape in a state where no external force is applied, and wherein the cathode diffusion layer protrudes in a thickness direction, from an outer circumferential portion toward a central portion thereof, and further protrudes in an opposite direction toward the central portion in a bowl shape in a state where no external force is applied.
5. The electrochemical pump according to claim 2, wherein an area of a curved surface of the anode diffusion layer which is in contact with the anode separator is larger than an area of the curved surface of the anode separator before the flow path groove is processed in a state where no external force is applied to the anode diffusion layer, and wherein an area of a curved surface of the cathode diffusion layer which is in contact with the cathode separator is larger than an area of the curved surface of the cathode separator before the flow path groove is processed in a state where no external force is applied to the cathode diffusion layer.
6. The electrochemical pump according to claim 1, wherein a thickness of the anode diffusion layer or the cathode diffusion layer is increased from an outer circumferential portion to a central portion.
7. An electrochemical pump comprising: an electrolyte membrane; a pair of plate-shaped diffusion layers disposed to be adjacent to both surfaces of the electrolyte membrane; and a pair of separators, each including a recess portion that accommodates one of the diffusion layers and pressing the one diffusion layer accommodated in the recess portion toward the electrolyte membrane, wherein a diameter of the one diffusion layer is smaller than a diameter of the respective recess portion in a state of not being pressed by the respective separator, and is equal to the diameter of the respective recess portion in a state of being pressed by the separator, and wherein a height of the one diffusion layer in a state of being pressed by the respective separator is lower than a height of the one diffusion layer in a state of not being pressed by the separator.
8. The electrochemical pump according to claim 7, wherein a central portion of the one diffusion layer is thicker than an outer circumferential portion of the one diffusion layer in a state of not being pressed by the respective separator.
9. The electrochemical pump according to claim 1, wherein a side surface of the first recess portion of the anode separator and a side surface of the anode diffusion layer are inclined with respect to a laminating direction at a contact portion between the anode separator and the side surface of the anode diffusion layer, so as to make room on an opposite side to the electrolyte membrane.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DESCRIPTION OF EMBODIMENTS
[0058] Hereinafter, embodiments of the disclosure will be described with reference to the drawings.
Embodiment 1
[0059]
[0060] <Overall Configuration>
[0061] In the electrochemical hydrogen pump 24 in Embodiment 1, both surfaces of an electrolyte membrane 2 on which an anode electrode layer 3 and a cathode electrode layer 4 are respectively formed are held between an anode diffusion layer 5 and a cathode diffusion layer 6, and outer sides of the anode diffusion layer 5 and the cathode diffusion layer 6 are held between an anode separator 7 and a cathode separator 8.
[0062] Further, outer sides of the anode separator 7 and the cathode separator 8 are held between an anode insulation plate 11 and a cathode insulation plate 12, and outer sides of the anode insulation plate 11 and the cathode insulation plate 12 are held between an anode end plate 13 and a cathode end plate 14. Further, the above-mentioned components are pressed by a press machine from outer sides of the anode end plate 13 and the cathode end plate 14 so as to be in close contact with each other.
[0063] The pressed state is maintained by bolts 15 and nuts 10. The seal 9 is attached around the anode diffusion layer 5 and the cathode diffusion layer 6 so that gas does not leak to the outside.
[0064] The electrolyte membrane 2 is a cation permeable membrane, and Nafion (registered trademark, manufactured by DuPont) and Aciplex (product name, manufactured by Asahi Kasei Corporation), for example, are used for the electrolyte membrane 2. The anode electrode layer 3 including, for example, a RuIrFeOx catalyst, is provided on an anode side surface of the electrolyte membrane 2, and the cathode electrode layer 4 including, for example, a platinum catalyst, is provided on a cathode-side surface of the electrolyte membrane 2.
[0065] The anode diffusion layer 5 is required to withstand the pressing of the electrolyte membrane 2 due to high-pressure hydrogen of a flow path groove 8a in the cathode separator 8. For this reason, a conductive porous body having sufficient rigidity, such as a titanium fiber sintered compact or a titanium powder sintered compact plated with platinum on surfaces thereof, is used as the anode diffusion layer 5.
[0066] A porous body, such as a graphitized carbon fiber (for example, performing graphitization by treating carbon fiber at a temperature of 2000 C. or higher), a titanium fiber sintered compact, or a titanium powder sintered compact having high elasticity and plated with platinum on surfaces thereof, is made to be paper-shaped and used as the cathode diffusion layer 6.
[0067] A product manufactured by compression molding fluoro-rubber is used as the seal 9. SUS316L plate materials, for example, in which flow path grooves 7a and 8a are formed by a cutting process are used as the anode separator 7 and the cathode separator 8.
[0068] <Anode Diffusion Layer 5 and Cathode Diffusion Layer 6>
[0069]
[0070] As shown in
[0071] As shown in
[0072] An apex of the central bowl shape is positioned lower than the outer circumferential portion by a dimension . A disc that is of a titanium fiber sintered compact or a titanium powder sintered compact plated with platinum on surfaces thereof and that has a thickness t1, for example, is used as the cathode diffusion layer 6. The cathode diffusion layer 6 is formed into such a shape by using the press molding method. The cathode diffusion layer 6 is used within a range of elastic deformation such that even when being deformed due to an external force, the cathode diffusion layer 6 can restore to an original shape once the external force is removed.
[0073]
[0074] <Anode Separator 7>
[0075] As shown in
[0076] As shown in
[0077] As shown in
[0078] As shown in
[0079] It is preferable that the diameter D1 of the recess portion 25 of the anode separator 7 and the diameter D1 of the recess portion 27 of the cathode separator 8 are larger than the diameter d1 of the anode diffusion layer 5 and the diameter d1 of the cathode diffusion layer 6. It is also preferable that the protrusion dimension 1 of the central portion of the anode diffusion layer 5 is larger than the protrusion dimension of the surface of the anode separator 7 which is in contact with the anode diffusion layer 5.
[0080] It is preferable that an area of a curved surface 29 of the anode diffusion layer 5 which is in contact with the anode separator 7 is larger than an area of the bottom surface 25a of the recess portion 25 of the anode separator 7 before the flow path groove 7a is processed, when no external force is applied to the anode diffusion layer 5.
[0081] It is preferable that an area of a curved surface 30 of the cathode diffusion layer 6 which is in contact with the cathode separator 8 is larger than an area of the bottom surface 27a of the recess portion 27 of the cathode separator 8 before the flow path groove 8a is processed, when no external force is applied to the cathode diffusion layer 6.
[0082] It is preferable that the thickness t1 of the anode diffusion layer 5 and the cathode diffusion layer 6 is about 10% thicker than the depth T1 in the vicinity of the side surface of the recess portion 25 of the anode separator 7 and the recess portion 27 of the cathode separator 8.
[0083] <Assembly Procedure>
[0084] Next, an assembly procedure of the electrochemical hydrogen pump 24 will be described.
[0085] First, the anode end plate 13 is placed on an assembly table (not shown). The anode insulation plate 11 and the anode separator 7 are laminated thereon. The anode diffusion layer 5 is placed on the anode separator 7, and the electrolyte membrane 2 is laminated thereon. At this time, the anode diffusion layer 5 having the diameter d1 is fitted to an inner side of the recess portion 25 of the anode separator 7 having the diameter D1.
[0086] Further, the cathode diffusion layer 6, the cathode separator 8, the cathode insulation plate 12 and the cathode end plate 14 are laminated sequentially on the electrolyte membrane 2. At this time, the seal 9 is fitted into the groove 28 of the cathode separator 8 in advance. The cathode diffusion layer 6 having the diameter d1 is fitted to an inner side of the recess portion 27 of the cathode separator 8 having the diameter D1.
[0087] <Compression Operation>
[0088] Next, the assembly table (not shown), on which the anode end plate 13 is placed, is installed in a press machine (not shown), and a compression force is applied by pressing the cathode end plate 14 downward toward the assembly table. In a state where the cathode end plate 14 is pressed toward the assembly table, the anode separator 7 and the cathode separator 8 press the anode diffusion layer 5 and the cathode diffusion layer 6 toward the electrolyte membrane 2.
[0089]
[0090] A portion, in the vicinity of the outer circumferential portion, of the curved surface 29 of the anode diffusion layer 5 is in contact with the anode separator 7, but the central portion of the curved surface 29 is not in contact with the anode separator 7. Similarly, a portion, in the vicinity of the outer circumferential portion, of the curved surface 30 of the cathode diffusion layer 6 is in contact with the cathode separator 8, but the central portion of the curved surface 30 is not in contact with the cathode separator 8.
[0091] An outer circumferential surface 5a of the anode diffusion layer 5 is not in contact with a side surface 25b of the recess portion 25 of the anode separator 7, and an outer circumferential surface 6a of the cathode diffusion layer 6 is not in contact with a side surface 27b of the recess portion 27 of the cathode separator 8.
[0092]
[0093] However, even at this stage, the central portion of the curved surface 29 of the anode diffusion layer 5 is still not in contact with the anode separator 7. Similarly, the central portion of the curved surface 30 of the cathode diffusion layer 6 is not in contact with the cathode separator 8.
[0094] Further, when the compression force is further applied as it is, the curved surface 29 of the anode diffusion layer 5 comes into contact with the anode separator 7 entirely as shown in
[0095] Before the compression force is applied, the area of the curved surface 29 of the anode diffusion layer 5 which is in contact with the anode separator 7 is larger than the area of the bottom surface 25a of the recess portion 25 before the flow path groove 7a of the anode separator 7 is processed. In other words, before the compression force is applied, the diameter d1 of the anode diffusion layer 5 is smaller than the diameter D1 of the recess portion 25 of the anode separator 7.
[0096] Therefore, at the time of compression, the anode diffusion layer 5 is pressed into the recess portion 25 of the anode separator 7 while being compressed in a direction orthogonal to a thickness direction. In other words, the anode diffusion layer 5 is disposed in the recess portion 25 in a compressed state. Since the outer circumferential surface 5a of the anode diffusion layer 5 is pressed against the side surface 25b of the recess portion 25 of the anode separator 7 by the compression force, the anode side gap 221 (see
[0097] Similarly, before the compression force is applied, the area of the curved surface 30 of the cathode diffusion layer 6 which is in contact with the cathode separator 8 is larger than the area of the bottom surface 27a of the recess portion 27 of the cathode separator 8 before the flow path groove 8a is processed. In other words, before the compression force is applied, the diameter d1 of the cathode diffusion layer 6 is smaller than the diameter D1 of the recess portion 27 of the cathode separator 8.
[0098] Therefore, the cathode diffusion layer 6 is pressed into the recess portion 27 of the cathode separator 8 while being compressed in a direction orthogonal to a thickness direction. In other words, the cathode diffusion layer 6 is disposed in the recess portion 27 in a compressed state. Since the outer circumferential surface 6a of the cathode diffusion layer 6 is pressed against the side surface 27b of the recess portion 27 of the cathode separator 8 by the compression force, the cathode side gap 222 (see
[0099] In such an electrochemical hydrogen pump 24, the electrolyte membrane 2 compresses the anode diffusion layer 5 in the thickness direction (direction of Y2) with the rise of the pressures of hydrogen filled in the flow path groove 8a and in gaps of the cathode diffusion layer 6. Further, the anode diffusion layer 5 presses a central portion of the anode separator 7 downward (compressing in the direction of Y2). At this time, the pressure of the high-pressure hydrogen acts on the anode diffusion layer 5 in a direction (direction of Y2) in which the anode diffusion layer 5 is close to be a flat plate.
[0100] Accordingly, as the pressure of hydrogen rises, a surface pressure between the outer circumferential surface 5a of the anode diffusion layer 5 and the side surface 25b of the recess portion 25 of the anode separator 7 rises greatly. Therefore, even when the pressure of hydrogen in the cathode separator 8 is high, a state in which the anode side gap 121 between the anode diffusion layer 5 and the anode separator 7 does not exist can be maintained.
[0101] <Evaluation Device>
[0102]
[0103] A gas-liquid separation device 36 and a cooling device 37 reduce the dew point of surplus hydrogen not used in the electrochemical hydrogen pump 24. The pressure on a high-pressure side is measured by a pressure gauge 38, and an exhaust valve 39 disposed downstream of the pressure gauge 38 is kept closed at usual times and opened when the pressure is equal to or greater than a predetermined value.
[0104] However, a degree to which the exhaust valve 39 is opened is adjusted so that a sufficient pressure loss occurs. That is, the degree to which the exhaust valve 39 is opened is set such that the pressure of hydrogen having passed through the exhaust valve 39 is reduced to approximately the atmospheric pressure (approximately 1.05 times the atmospheric pressure) by the pressure loss occurring at the exhaust valve 39.
[0105] The dew point of hydrogen reduced to approximately the atmospheric pressure is lowered by the gas-liquid separation device 36 and the cooling device 37. The hydrogen whose pressure has been reduced is diluted in a dilution device 41 by nitrogen supplied from a nitrogen cylinder 40, and then discharged to an exhaust port 42 leading to the outside.
[0106] In the subsequent evaluation process, a temperature of the heater 35 is set to 65 C., and a temperature of the cooling device 37 is set to 20 C.
[0107] <Evaluation Process>
[0108] A process for evaluating the electrochemical hydrogen pump 24 will be described.
[0109] (1) As shown in
[0110] (2) A three-way valve 43 is switched from an atmosphere opening position (arrow A) to a closed side (arrow B).
[0111] (3) A valve 44 of the nitrogen cylinder 40 for dilution is operated to allow the nitrogen to flow into the dilution device 41.
[0112] (4) A valve 45 of the hydrogen cylinder 32 and the regulator 33 are operated to supply low-pressure (pressure ratio of 0.05) hydrogen to the electrochemical hydrogen pump 24. The pressure ratio is a ratio of an actually applied pressure to a predetermined pressure.
[0113] (5) The power source 120 is turned ON, and an electrode area is calculated to set a current value such that a current density is 1.0 (A/cm.sup.2).
[0114] (6) Voltages displayed at the power source 120 are recorded every time the pressure ratio increases by 0.05 until the pressure displayed by the pressure gauge 38 reaches a target pressure (pressure ratio of 1.0).
[0115] (7) The power source 120 is turned OFF, and each valve is operated to stop the supply of hydrogen, and then a supply of nitrogen for dilution is stopped.
[0116] (8) Finally, the three-way valve 43 is switched from the closed position (arrow B) to the atmosphere opening side (arrow A).
[0117] (9) The electrochemical hydrogen pump 24 in Embodiment 1 is removed.
[0118] <Evaluation Result>
[0119]
[0120] In the related-art electrochemical hydrogen pump 23 described in Patent Document 1, the voltage ratio gradually increases from a pressure ratio of 0.05 to a pressure ratio of 0.6, and the voltage ratio increases rapidly from the pressure ratio of 0.6 to a pressure ratio of 1.0. In the electrochemical hydrogen pump 24 in Embodiment 1, the voltage ratio gradually increases until the pressure ratio reaches 0.6, and then the voltage ratio increases rapidly. This tendency of the electrochemical hydrogen pump 24 is the same as that of the related-art electrochemical hydrogen pump 23.
[0121] However, the voltage ratio of the electrochemical hydrogen pump in Embodiment 1 is lower than that of the related-art electrochemical hydrogen pump 23 by about 0.2 points in a range of the pressure ratio from 0.05 to 0.6, and the performance is improved. In a range of the pressure ratio from 0.6 to 1.0, the difference between the voltage ratio of the electrochemical hydrogen pump 24 in Embodiment 1 and the voltage ratio of the related-art electrochemical hydrogen pump 23 is expanded. That is, when the electrochemical hydrogen pump 24 in Embodiment 1 and the related-art electrochemical hydrogen pump 23 are compared, it can be said that the performance of the electrochemical hydrogen pump 24 is particularly improved when the pressure on the cathode side rises.
[0122] The reason why the voltage ratio of the related-art electrochemical hydrogen pump 23 is higher is considered to be the diffusion of concentrated hydrogen from the cathode side gap 222 toward the anode side gap 221 in the electrochemical hydrogen pump 23. That is, the performance of the electrochemical hydrogen pump 24 in Embodiment 1 is improved since improvement has been made in that point.
[0123] In
Embodiment 2
[0124]
[0125] <Overall Configuration>
[0126] In the electrochemical hydrogen pump 46, since high-pressure hydrogen needs to be stored on a cathode side, the following problems arise. That is, central portions of a cathode end plate 14, a cathode insulation plate 12 and a cathode separator 8 are displaced upward (direction of Y1) in
[0127] Since contact surface pressures between the cathode diffusion layer 6 and a cathode electrode layer 4, and between the cathode diffusion layer 6 and the cathode separator 8, in the vicinity of the center, are lower than that of the surrounding due to the displacement, the contact resistance increases and the voltage rises. As a result, the performance of an electrochemical hydrogen pump decreases.
[0128] It is considered that this is the reason why the voltage ratio increases rapidly from a pressure ratio of 0.6 to a pressure ratio of 1.0 in the evaluation results of the electrochemical hydrogen pump 23 in Patent Document 1 and the electrochemical hydrogen pump 24 in Embodiment 1 as shown in
[0129] Generally, a measure of increasing the thickness of the cathode end plate 14 and the anode end plate 13 to improve the rigidity thereof is generally adopted so as not to affect the performance by the displacement. However, such a measure leads to other problems that weights of the members become extremely heavy and that handling of each member becomes difficult.
[0130] Therefore, in the electrochemical hydrogen pump 46 in Embodiment 2, the cathode diffusion layer 6 is formed to be thicker at the center thereof.
[0131] A thickness of an outer circumferential portion of the cathode diffusion layer 6 is t1, and a thickness of the central portion is t4 (t1<t4). For example, t4 is 1.05 times of t1. Accordingly, the contact surface pressures between the cathode diffusion layer 6 and the cathode electrode layer 4, and between the cathode diffusion layer 6 and the cathode separator 8 become larger at the central portion of the cathode diffusion layer 6.
[0132] Therefore, even in a case where each component displaces in the direction of Y1 and the direction of Y2 with the rise of the pressure of hydrogen on the cathode side, the contact surface pressures between the cathode diffusion layer 6 and the cathode separator 8, and between the cathode diffusion layer 6 and the cathode electrode layer 4 can be substantially the same at the outer circumferential portion and the central portion of the cathode diffusion layer 6. Therefore, the performance of the electrochemical hydrogen pump 46 does not decrease. That is, decrease in performance of the electrochemical hydrogen pump 46 can be prevented without increasing the thickness of the cathode end plate 14 and the anode end plate 13.
[0133] <Evaluation>
[0134] In
[0135] As shown in
[0136] It is because a decrease in the contact surface pressures between the cathode diffusion layer 6 and the cathode separator 8, and between the cathode diffusion layer 6 and the cathode electrode layer 4 is prevented as compared with that in Embodiment 1 even when the pressure of hydrogen on the cathode side rises.
[0137] That is, in the electrochemical hydrogen pump 46 in Embodiment 2, there is no need to increase the thickness of the cathode endplate 14 and the anode end plate 13.
Embodiment 3
[0138]
[0139] <Overall Configuration>
[0140] In Embodiment 1, as shown in
[0141] Therefore, as shown in
[0142] Accordingly, on a side of the electrolyte membrane 2, the side surface 25b of the recess portion 25 of the anode separator 7 and the outer circumferential surface 5a of the anode diffusion layer 5 are reliably brought into close contact in a ridge line of the anode diffusion layer 5 on the side of the electrolyte membrane 2. According to this configuration, even if there are variations in manufacturing, the outer circumferential surface 5a of the anode diffusion layer 5 can be reliably brought into close contact with the side surface 25b of the recess portion of the anode separator 7 on the side of the electrolyte membrane 2, so that the electrolyte membrane 2 can be prevented from hanging down in a skimmer even when the pressure of hydrogen on the cathode side is high.
[0143] <Evaluation>
[0144] In
[0145] The electrochemical hydrogen pump of the disclosure has the following characteristics.
[0146] An anode diffusion layer 5 is generally disc-shaped, and a central portion thereof protrudes in a bowl shape when no external force is applied.
[0147] A cathode diffusion layer 6 is generally disc-shaped, and protrudes in a thickness direction, from an end portion toward a central portion thereof, and then protrudes in an opposite direction to a bowl shape in the vicinity of the center when no external force is applied. An apex of the central bowl shape is positioned lower than an outer circumferential portion.
[0148] An anode separator 7 is generally disc-shaped. A surface of the anode separator 7 in contact with the anode diffusion layer 5 has a recess portion 25 that accommodates the anode diffusion layer 5. A depth of the recess portion 25 is not constant, and a bottom surface 25a is a bowl-shaped curved surface having a protruding central portion.
[0149] A cathode separator 8 is generally disc-shaped. A surface of the cathode separator 8 in contact with the cathode diffusion layer 6 has a recess portion 27 that accommodates the cathode diffusion layer 6. A depth of the recess portion 27 is not fixed, and a bottom surface 27a is a bowl-shaped curved surface having a recessed central portion.
[0150] An area of a curved surface 29 of the anode diffusion layer 5 which is in contact with the anode separator 7 is larger than an area of the bottom surface 25a of the recess portion 25 of the anode separator 7 before a flow path groove 7a is processed.
[0151] An area of a curved surface 30 of the cathode diffusion layer 6 which is in contact with the cathode separator 8 is larger than an area of the bottom surface 27a of the recess portion 27 of the cathode separator 8 before a flow path groove 8a is processed.
[0152] Further, the thickness of the anode diffusion layer 5 or the cathode diffusion layer 6 is increased from the outer circumferential portion to the center thereof. In the vicinity of a contact portion between a side surface 25b of the recess portion 25 of the anode separator 7 and the outer circumferential surface 5a of the anode diffusion layer 5, there is an anode side gap 421 on a side opposite to the electrolyte membrane 2.
[0153] According to the above-described characteristics, there are no gaps between the anode diffusion layer 5 and the anode separator 7, and between the cathode diffusion layer 6 and the cathode separator 8, and the electrolyte membrane 2 is not exposed to hydrogen. Therefore, decrease in performance of the electrochemical hydrogen pump due to diffusion of concentrated hydrogen from a high-pressure side to a low-pressure side is prevented.
[0154] Further, even when the pressure of hydrogen on a cathode side rises, a decrease in contact surface pressures between the cathode diffusion layer 6 and the cathode separator 8, as well as in contact surface pressures between the cathode diffusion layer 6 and the cathode electrode layer 4 is prevented. Accordingly, the electrochemical hydrogen pump of the disclosure is optimal as a hydrogen compressing device for a small home hydrogen filling device.
[0155] The electrochemical hydrogen pump of the disclosure can be used as a hydrogen compressing device for a hydrogen filling device. Further, the structure of the electrochemical hydrogen pump of the disclosure can be used as an electrochemical water electrolysis device which produces hydrogen and oxygen by electrolysis of water.