The present invention relates to a redox flow battery, Priority is claimed on Japanese Patent Application No. 2016-153696, filed on Aug. 4, 2016, the content of which is incorporated herein by reference.
As a large-capacity storage battery, a redox flow battery is known. Typically, the redox flow battery includes an ion-exchange membrane configured to separate an electrolytic solution, and an electrode that is provided on both sides of the ion-exchange membrane. In the redox flow battery, an oxidation reaction and a reduction reaction are simultaneously performed in the electrodes, and thus charging and discharging are performed.
In the redox flow battery, a reduction of internal resistance (cell resistance) and a reduction of a pressure loss when the electrolytic solution permeates through the electrodes are required so as to enhance energy efficiency of the entirety of the redox flow battery.
For example, Patent Document 1 and Patent Document 2 achieve a reduction of a pressure loss by providing a groove that becomes a flow passage of an electrolytic solution in a current collector plate.
The redox flow battery shown in
The redox flow battery shown in
Patent Document 1: Japanese Unexamined Patent Application, First Publication No. 2015-122231
Patent Document 2: Published Japanese Translation No. 2015-505147 of the PCT International Publication
The differences of a flow state of the electrolytic solution caused in a plane of the electrode causes an increase in cell resistance of a redox flow battery. The reason is that the entire surface of the electrode cannot be used to the maximum, when charging/discharging is performed. Accordingly, a configuration of a redox flow battery is required wherein an electrolytic solution can be supplied uniformly in an in-plane direction of an electrode.
One aspect of the present invention has been made in consideration of the above-described problem, and an object of the present invention is to provide a redox flow battery which does not include a part in which an electrolytic solution does not flow uniformly, and cell resistance thereof is low.
The present inventors found that, by locating an electrode at a predetermined position with respect to a current collector plate, it is possible to prevent the formation of a short-circuit passage at which a short circuit is caused by an electrolytic solution and to uniformize the flow of the electrolytic solution. Then, they found that cell resistance can be decreased by uniformizing the flow of the electrolytic solution.
Namely, one aspect of the present invention provides means described below to solve the above-described problem.
(1) A redox flow battery according to the first aspect is a redox flow battery which includes: an ion-exchange membrane; a current collector plate; and an electrode that is disposed between the ion-exchange membrane and the current collector plate, wherein charging and discharging are performed by flowing of an electrolytic solution to the electrode. The electrode includes a first electrode part and a second electrode part in this order from the current collector plate side. The area of the second electrode part is larger than the area of the first electrode part and the second electrode part covers the whole of the first electrode part, when viewed from the ion-exchange membrane side. The current collector plate has a peripheral edge wall, which forms a housing region to which the first electrode part fits, on a surface of the electrode side of the current collector plate. The second electrode part covers at least a part of a surface of the peripheral edge wall of the ion-exchange membrane side.
(2) In the redox flow battery according to the aforementioned aspect, the second electrode part may cover the whole of the surface of the peripheral edge wall of the ion-exchange membrane side.
(3) In the redox flow battery according to the aforementioned aspect, the first electrode part and the second electrode part may be constituted by different conductive sheets.
(4) In the redox flow battery according to the aforementioned aspect, transmittance of an electrolytic solution at the second electrode part may be smaller than transmittance of an electrolytic solution at the narrow part.
(5) In the redox flow battery according to the aforementioned aspect, the second electrode part may be a carbon nanotube sheet including carbon nanotubes having an average fiber diameter of 1 μm or less, and the first electrode part may be carbon paper or carbon felt including carbon fibers having an average fiber diameter of 1 μm or more.
(6) In the redox flow battery according to the aforementioned aspect, areas which are surrounded by the peripheral edge wall may be arranged in parallel.
(7) In the redox flow battery according to the aforementioned aspect, the electrode may have a conductive sheet on the ion-exchange membrane side of the second electrode part.
(8) In the redox flow battery according to the aforementioned aspect, the peripheral edge wall may include a first step part which supports the second electrode part and a second step part which supports the conductive sheet which is provided on the ion-exchange membrane side of the second electrode part.
Due to the redox flow battery according to the one aspect of the invention, it is possible to prevent the formation of a short-circuit passage which causes uneven flow of an electrolytic solution.
Hereinafter, a redox flow battery will be described in detail with reference to the accompanying drawings.
In the drawings used in the following description, for convenience, characteristic portions may be enlarged for easy understanding of the characteristics of the invention, and dimensions, ratios and the like of respective constituent elements may be different from actual dimensions. Materials, dimensions, and the like exemplified in the following description are illustrative only, and the present invention is not limited thereto and can be embodied in appropriately modified manners in a range that does not change the gist thereof.
The redox flow battery 100 illustrated in
The redox flow battery 100 illustrated in
Hereinafter, a stacking direction of the cell stack structure in which the cells CE are stacked may be referred to as “stacking direction”, and a plane direction perpendicular to the stacking direction of the cell stack structure may be referred to as “in-plane direction”.
Ion-Exchange Membrane
As the ion-exchange membrane 10, a positive ion-exchange membrane can be used. Specific examples of materials of the positive ion-exchange membrane include a perfluorocarbon polymer having a sulfonic acid group, a hydrocarbon-based polymer compound having a sulfonic acid group, a polymer compound doped with an inorganic acid such as phosphorous acid, an organic/inorganic hybrid polymer of which a part is substituted with a proton-conductive functional group, and a proton conductor in which a polymer matrix is impregnated with a phosphoric acid solution or a sulfuric acid solution. Among these, the perfluorocarbon polymer having a sulfonic acid group is preferable, and Napion (registered trademark) is more preferable.
Current Collector Plate
The current collector plate 20 is a current collector that plays a role of delivering and receiving an electron to and from the electrode 30. The current collector plate 20 may be referred to as a “bipolar plate”.
For example, a conductive material containing carbon can be used for the current collector plate 20 as a material having conductivity. Specific examples of the conductive material include a conductive resin including graphite and an organic polymer compound, a conductive resin in which a part of graphite is substituted with at least one of carbon black and diamond-like carbon, and a shaped material obtained through kneading of carbon and a resin and shaping the kneaded material. Among these, it is preferable to use the shaped material obtained through kneading of carbon and a resin and shaping the kneaded material.
A peripheral edge wall 21 which surrounds a recessed portion 20A is provided on a surface of the current collector plate 20 on the ion-exchange membrane 10 side. An electrolytic solution is supplied into the recessed portion 20A, which is surrounded by the peripheral edge wall 21, from an opening 21i of the peripheral edge wall 21. In the recessed portion 20A, an area to which a part of the electrode 30 is accommodated is an accommodation area 20B. The accommodation area 20B is formed by the peripheral edge wall 21 and an inner wall 22 in
The inner wall 22 is provided in the recessed portion 20A surrounded by the peripheral edge wall 21. The inner wall 22 forms a first flow passage C in which an electrolytic solution flows at an inflow part. The flow passage C formed by the inner wall 22 is not limited.
The inner wall 22 shown in
Here, the configuration of the current collector plate 20 is not limited to the configuration shown in
Electrode
The electrode 30 includes a first electrode part 31 and a second electrode part 32 in this order from the current collector plate 20 side. The second electrode part 32 covers the whole of the first electrode part 31 when viewed from the ion-exchange membrane 10 side. The area of the second electrode part 32 is larger than the area of the first electrode part 31. Hereinafter, the first electrode part 31 may be described as a narrow part, and the second electrode part 32 may be described as a wide part.
In
The narrow part 31 and the wide part 32 may be integrated with each other, or may be formed as a laminate in which different conductive sheets are laminated.
The wide part 32 is located on the top surface 21a of the peripheral edge wall 21. The wide part 32 may cover at least a part of the top surface 21a, and it is preferable that the wide part 32 cover the whole of the top surface 21a. When the wide part 32 covers the top surface 21a, it is possible to prevent the formation of a short-circuit passage regarding the flow of an electrolytic solution described below.
As the electrode 30, a conductive sheet including carbon fibers can be used. The carbon fibers stated here are fiber-shaped carbon, and examples thereof include carbon fiber, carbon nanotubes and the like. When the electrode 30 includes the carbon fibers, a contact area between the electrolytic solution and the electrode 30 increases, and thus reactivity of the redox flow battery 100 is enhanced. Particularly, when the electrode 30 includes carbon nanotubes having a diameter of 1 μm or less, it is possible to enlarge the contact area of the electrolytic solution, and thus such a structure is preferable. Such an effect is obtained because of the small fiber diameter of the carbon nanotube. When the electrode 30 includes carbon fibers having a diameter of 1 μm or greater, the conductive sheet is strong and is less likely to be fractured, and thus such a structure is preferable. As the conductive sheet including the carbon fibers, for example, carbon felt, carbon paper, a carbon nanotube sheet and the like can be used.
It is preferable that the liquid permeability of the narrow part 31 be higher than that of the wide part 32. When the liquid permeability of the narrow part 31 is higher than that of the wide part 32, an electrolytic solution that has entered in the electrode chamber K is blocked by the wide part 32, and is diffused in an in-plane direction. When the electrolytic solution is diffused in an in-plane direction of the entire surface of the recessed portion 20A, it is possible to perform a charging/discharging reaction using the entire surface of the electrode 30, the cell resistance decreases, and charging discharging capacity increases.
Here, the liquid permeability can be evaluated by Darcy's law of permeability (hereinafter, may be simply referred to as “permeability”). Darcy's law is generally used to indicate permeability of a porous medium, but is also applied to members other than the porous material in the invention for convenience. At this time, with respect to a non-uniform and anisotropic member, permeability in a direction in which the lowest permeability is obtained is employed.
Darcy's permeability k (m2) is calculated from a relationship of a liquid permeation flux (m/sec) expressed by the following expression, using a cross-sectional area S (m2) of a member through which a liquid having viscosity μ (Pa·sec) permeates, a length L (m) of the member, and a differential pressure ΔP (Pa) between a liquid inflow side and a liquid outflow side of the member when a liquid passes therethrough in a flow rate of Q (m3/sec).
The liquid permeability in the narrow part 31 is preferably 100 or more times the permeability of the wider part 32, more preferably 300 or more times, and still more preferably 1000 or more times. Concrete Examples which can achieve such a relationship include a case wherein carbon paper, carbon felt or the like, which is formed by carbon fibers or the like having an average fiber diameter of 1 μm or more, is used as the narrow part 31, and a carbon nanotube sheet or the like including carbon nanotubes or the like having an average fiber diameter of 1 μm or less is used as the wide part 32. The permeability in the narrow part 31 represents permeability in an in-plane direction. The permeability in the wide part 32 represents permeability in a stacking direction (a normal direction perpendicular to the in-plane direction).
Operation of a Redox Flow Battery
Using
In the electrode chamber K of the redox flow battery 100, an electrolytic solution is supplied from an inflow port provided at the cell frame 40. The electrolytic solution which is supplied to the electrode chamber K reacts with the electrode 30 in the electrode chamber K. Ions which are generated by the reaction circulate between the electrodes 30 via the ion-exchange membrane 10, and thus charging and discharging are performed. The electrolytic solution after the reaction is discharged from an outflow port provided at cell frame 40.
In the electrode chamber K, the electrolytic solution is supplied into the recessed portion 20A from an opening 21i of the peripheral edge wall 21 (flow f11). The supplied electrolytic solution flows along the inner wall 22 and is diffused in an in-plane direction of the recessed portion 20A (flow f12). Then, the solution is discharged from a discharge passage 23 through the electrode 30 (flow f13).
Hereinafter, a flow of an electrolytic solution from the recessed portion 20A to the discharge passage 23 is concretely explained.
Here, it is considered that a short-circuit passage may be formed such that, after the electrolytic solution passes through the interface of the narrow part 31 and the peripheral edge wall 21, the electrolytic solution does not pass through the inside of the electrode 30 but passes through the interface of the wide part 32 and the top surface of the peripheral edge wall 21. However, since a pressure is applied in a stacking direction of the cell, and a gap between the peripheral edge wall 21 and the electrode 30 is small, such a short-circuit passage is less likely to be formed at the position. Furthermore, a flow direction of the electrolytic solution which passes through the interface of the narrow part 31 and the peripheral edge wall 21 intersects a flow direction of the electrolytic solution which passes through the interface of the top surface of the peripheral edge wall 21 and the wide part 32, and therefore such a short-circuit passage is hardly generated.
On the other hand,
As shown in
Liquid distribution resistance of the short-circuit passage is lower than that of the flow passage which arrives at the discharge passage 23 through the electrode 35. Accordingly, a large amount of the electrolytic solution flows to the discharge passage 23 via the short-circuit passage. When a large amount of the electrolytic solution flows in the short-circuit passage, the flow of the electrolytic solution becomes uneven, and the electrolytic solution is not diffused uniformly all over the plane. Thus, the whole surface of the electrode cannot contribute to a reaction, and cell resistance increases.
Furthermore,
In the redox flow battery shown in
In addition, in the redox flow battery shown in
As described above, due to the redox flow battery 100 according to the first aspect, it is possible to avoid the formation of a short circuit at which the electrolytic solution does not pass through. Accordingly, in the redox flow battery 100 according to the first embodiment, the electrolytic solution can be supplied uniformly in an in-plane direction, and cell resistance decreases.
The electrode 37 of the redox flow battery shown in
The liquid permeability of the conductive sheet 33 is preferably 100 or more times the permeability of a wide part 32, more preferably 300 or more times, and still more preferably 1000 or more times. Concrete Examples which can achieve such a relationship include a case wherein a carbon sheet or the like including carbon nanotubes or the like having an average fiber diameter of 1 μm or less is used as the wide part 32, and carbon paper, carbon felt or the like, which is formed by carbon fibers or the like having an average fiber diameter of 1 μm or more, is used as the conductive sheet 33. The liquid permeability of the conductive sheet 33 represents permeability in an in-plane direction. On the other hand, the liquid permeability of the wide part 32 represents permeability in a stacking direction (a normal direction perpendicular to the in-plane direction).
In a case where the liquid permeability of the conductive sheet 33 is sufficiently higher than the liquid permeability of the wide part 32, the electrolytic solution that passes through the wide part 32 does not stay in the conductive sheet 33, and rapidly flows to the outflow port side. The electrolytic solution not staying in the conductive sheet 33 refers to a pressure necessary for the electrolytic solution to pass through the conductive sheet 33 being sufficiently lower than a pressure necessary for the electrolytic solution to pass through the wide part 32.
That is, since the electrolytic solution can be discharged efficiently from the inside of the conductive sheet 33, it is possible to prevent a flow of the electrolytic solution, which flows in the wide part 32 in a vertical direction (stacking direction), from being disturbed.
Furthermore, in the redox flow battery shown in
Accordingly, when viewed from the ion-exchange membrane 10 side, the interface of the narrow part 31 and the first step part 21A is blocked by the wide part 32, and the interface of the wide part 32 and the second step part 21B is blocked by the conductive sheet 33. In a case that the electrolytic solution flows along the surface of the first step part 21A and the second step part 21B, it is necessary for the electrolytic solution to flow while changing the flowing direction of the electrolytic solution.
As described above, the redox flow battery according to the second embodiment prevents the formation of a short-circuit passage due to the first step part 21A and the second step part 21B. As a result, the electrolytic solution is supplied uniformly all over the plane, and the cell resistance of the redox flow battery can decrease:
The redox flow battery according to the first embodiment and the redox flow battery according to the second embodiment can be suitably used according to use, material used thereof and the like. The redox flow battery according to the first embodiment is superior to the redox flow battery according to the second embodiment from the viewpoint of ease of processing.
While preferred embodiments of the invention have been described above, it should be understood that the present invention is not limited to the specific embodiments, and may be changed and modified within the scope of the summary of the present invention which is described in the appended claims.
10 Ion-exchange membrane
20 Current collector plate
20A Recessed portion
20B Accommodation area
21 Peripheral edge wall
21
a Top surface
21A First step part
21B Second step part
22 Inner wall
23 Discharge passage
30, 35, 36, 37 Electrode
35A, 36A First electrode layer
35B, 36B Second electrode layer
31 First electrode part (narrow part)
32 Second electrode part (wide part)
33 Conductive sheet
40 Cell frame
100 Redox flow battery
CE Cells
K Electrode chamber
C Flow passage
C1 First flow passage
C2 Second flow passage
E Electrode
Number | Date | Country | Kind |
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2016-153696 | Aug 2016 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2017/028436 | 8/4/2017 | WO | 00 |