The present invention relates to a cell frame and a redox flow battery.
Conventionally, as a secondary battery for energy storage, a redox flow battery is known which is charged and discharged through a redox reaction of active materials contained in an electrolyte solution. The redox flow battery has features such as easy increase in capacity, long life, and accurate monitoring of its state of charge. Because of these features, in recent years, the redox flow battery has attracted a great deal of attention, particularly for application in stabilizing the output of renewable energy whose power production fluctuates widely or leveling the electric load.
In the meantime, to obtain a predetermined voltage, the redox flow battery is generally configured to include a cell stack having a plurality of cells that are stacked. However, such a configuration has a problem that a current loss (i.e. shunt current loss) is generated through the electrolyte solution. As one of methods for reducing the shunt current loss, there is known a method for increasing the electrical resistance of the electrolyte solution in a slit (i.e. flow channel) provided in a cell frame that constitutes the cell, and many proposals have been made using this method. Patent Literature 1 proposes a method for reducing the shunt current loss by changing the flow channel structure for each cell frame so as to increase the electrical resistance of the electrolyte solution from the center toward the end of the cell stack in the stacking direction thereof. Patent Literature 2 proposes a method for reducing the shunt current loss by incorporating a structure of forming droplets of the electrolyte solution into the flow channel of the cell frame and thus by forming an insulating space of air in the flow channel, so as to increase the electrical resistance of the electrolyte solution.
In the method described in Patent Literature 1, the cell frames having different flow channel structures must be prepared and stacked in an appropriate order to form the cell stack, and therefore the manufacturing process becomes complicated. Further, in this method, the length of the slit is changed for each cell frame to change the electrical resistance of the electrolyte solution. Therefore, the flow rate of the electrolyte solution may differ significantly between the cell frames (cells), which is considered undesirable for performing stable operation (charge/discharge process). On the other hand, in the method described in Patent Literature 2, the flow channel structure for forming droplets of the electrolyte solution becomes complicated, and a complicated operation control is also needed to ensure formation of the insulating space of air, such as need for appropriate management of the droplet volume of the electrolyte solution.
It is therefore an object of the present invention to provide a cell frame and a redox flow battery in which the shunt current loss can be reduced with a simple configuration.
To achieve the above object, a cell frame according to the present invention includes: a frame body having an opening, the frame body including a through-hole for passage of a fluid containing an active material, the through-hole penetrating from one surface of the frame body to the other surface thereof around the opening, and a groove-like slit formed in the one surface or the other surface and connecting the through-hole and the opening; and a rotor made of an insulating material, the rotor received in the slit and forced to rotate by a flow of the fluid through the slit between the through-hole and the opening.
According to an aspect of the present invention, a redox flow battery includes a cell stack having a plurality of stacked cells, wherein at least one of a plurality of cell frames that forms the plurality of cells is the cell frame as described above.
According to another aspect of the present invention, a redox flow battery includes a cell stack having a plurality of stacked cells, wherein the cell stack is divided into a plurality of cell groups each of which consists of the plurality of cells, the plurality of cell groups is connected to each other such that a fluid containing an active material flows in parallel through the plurality of cell groups, and the plurality of cells in each of the cell groups is connected to each other such that the fluid flows in series or in parallel through the plurality of cells, and wherein the redox flow battery comprises a rotor received in at least one of a plurality of passage that are respectively connected to the plurality of cell groups, the rotor made of an insulating material and forced to rotate by a flow of the fluid through the at least one flow passage.
According to the cell frame and the redox flow battery, it is possible to increase the electrical resistance of the fluid (i.e. electrolyte solution) in the slit (i.e. flow channel) without significantly affecting the flow rate of the fluid (i.e. electrolyte solution) flowing through the slit (i.e. flow channel). Further, since only installation of the rotor in the slit (i.e. flow channel) is required, the flow channel structure does not become complicated, and a complicated operation control is not needed.
As described above, according to the present invention, the shunt current loss can be reduced with a simple configuration.
Embodiments of the present invention will be described below with reference to the drawings.
Redox flow battery 1 is configured to be charged and discharged through a redox reaction of positive- and negative-electrode active materials in cell 10, and includes cell stack 2 having a plurality of stacked cells 10. Cell stack 2 is connected to positive electrode-side tank 3 for storing a positive electrolyte solution through positive electrode-side incoming pipe L1 and positive electrode-side outgoing pipe L2. Positive electrode-side incoming pipe L1 is provided with positive electrode-side pump 4 for circulating the positive electrolyte solution between positive electrode-side tank 3 and cell stack 2. Cell stack 2 is connected to negative electrode-side tank 5 for storing a negative electrolyte solution through negative electrode-side incoming pipe L3 and a negative electrode outgoing pipe L4. Negative electrode-side incoming pipe L3 is provided with negative electrode-side pump 6 for circulating the negative electrolyte solution between negative electrode-side tank 5 and cell stack 2. As the electrolyte solution, any fluid containing an active material may be used, such as a slurry formed by suspending and dispersing a granular active material in a liquid phase, or a liquid active material itself. Therefore, the electrolyte solution described herein is not limited to a solution of an active material.
Cells 10 are separated from each other by a cell frame described below. A detailed configuration of the cell frame will be described below. Although four cells 10 are shown in
Each of cells 10 includes positive cell 11 that houses positive electrode 11a, negative cell 12 that houses negative electrode 12a, and membrane 13 that separates positive cell 11 and negative cell 12. Positive cell 11 is connected to positive electrode-side incoming pipe L1 through individual supply flow channel P1 and common supply flow channel C1, and is connected to positive electrode-side outgoing pipe L2 through individual return flow channel P2 and common return flow channel C2. This allows positive cell 11 to be supplied with the positive electrolyte solution containing the positive-electrode active material from positive electrode-side tank 3. Thus, in positive cell 11, an oxidation reaction occurs during a charge process in which the positive-electrode active material changes from a reduced state to an oxidized state, and a reduction reaction occurs during a discharge process in which the positive-electrode active material changes from the oxidized state to the reduced state. On the other hand, negative cell 12 is connected to negative electrode-side incoming pipe L3 through individual supply flow channel P3 and common supply flow channel C3, and is connected to negative electrode-side outgoing pipe L4 through individual return flow channel P4 and common return flow channel C4. This allows negative cell 12 to be supplied with the negative electrolyte solution containing the negative-electrode active material from negative electrode-side tank 5. Thus, in negative cell 12, a reduction reaction occurs during the charge process in which the negative-electrode active material changes from an oxidized state to a reduced state, and an oxidation reaction occurs during the discharge process in which the negative-electrode active material changes from the reduced state to the oxidized state.
As described above, cell frame 20 separates adjacent cells 10 from each other, and includes frame 21 and bipolar plate 23 mounted to opening 22 of frame 21. A space inside opening 22 is divided by bipolar plate 23 into two compartments, one of which (i.e. compartment on a side facing out of the page) houses positive electrode 11a and the other of which (i.e. compartment on a side facing into the page) houses negative electrode 12a. In other words, positive cell 11 for housing positive electrode 11a is formed between one surface of bipolar plate 23 and membrane 13, and negative cell 12 for housing negative electrode 12a is formed between the other surface of bipolar plate 23 and membrane 13.
Frame body 21 includes through-holes 31-34 that are formed near the four corners thereof around opening 22 and that penetrate respectively from one surface of frame body 21 to the other surface thereof in its thickness direction. Once cell frames 20 are stacked to form cell stack 2, through-holes 31-34 respectively constitute common flow channels C1-C4 as described above, through which the electrolyte solution flows. Specifically, through-hole 31 on the lower left corner and through-hole 32 on the upper right corner respectively constitute common supply flow channel C1 and common return flow channel C2 for the positive electrolyte solution, and through-hole 33 on the lower right corner and through-hole 34 on the upper left corner respectively constitute common supply flow channel C3 and common return flow channel C4 for the negative electrolyte solution.
Frame body 21 includes groove-like slits 35, 36 that are formed on one surface (i.e. surface facing out of the page) and that connect through-holes 31, 32 to a portion of opening 22 for receiving positive electrode 11a. Once cell frames 20 are stacked to form cell stack 2, slits 35, 36 respectively constitute individual flow channels P1, P2 for the positive electrolyte solution as described above. Therefore, the positive electrolyte solution is supplied from through-hole 31 (common supply flow channel C1) to the portion of opening 22 that receives positive electrode 11a (positive cell 11) through slit 35 (individual supply flow channel P1), and is returned to through-hole 32 (common return flow channel C2) through slit 36 (individual return flow channel P2).
Further, frame body 21 includes groove-like slits 37, 38 that are formed on the other surface (i.e. surface facing into the page) and that connect through-holes 33, 34 to a portion of opening 22 for receiving negative electrode 12a. Once cell frames 20 are stacked to form cell stack 2, slits 37, 38 respectively constitute individual flow channels P3, P4 for the negative electrolyte solution as described above. Therefore, the negative electrolyte solution is supplied from through-hole 33 (common supply flow channel C3) to the portion of opening 22 that receives negative electrode 12a (negative cell 12) through slit 37 (individual supply flow channel P3), and is returned to through-hole 34 (common return flow channel C4) through slit 38 (individual return flow channel P4).
Further, cell frame 20 includes cross-shaped rotor 40 made of an insulating material that is received in slit 35. Cross-shaped rotor 40 can be forced to rotate by the flow of the electrolyte solution through slit 35 between through-hole 31 and opening 22, as described in detail below. Although not described and illustrated herein, the remaining slits 36-38 of four slits 35-38 are also provided with the same cross-shaped rotor 40 (including a variation thereof described below).
Cross-shaped rotor 40 is received in rotor receiving recess 50 which is a portion of slit 35 that is wider than the other portions thereof, and has a constant width corresponding to the depth of rotor receiving recess 50 (i.e. length along the thickness direction of frame body 21 perpendicular to the page). The depth of rotor receiving recess 50 may or may not be the same as the depth of slit 35, but is preferably the same as or larger than the depth of slit 35 from the viewpoint of preventing an unnecessary pressure drop when the electrolyte solution passes through rotor receiving recess 50.
Cross-shaped rotor 40 includes elongated base 41, a pair of main vanes 42, 43, and a pair of auxiliary vanes 44, 45. Base 41 includes long hole 41a extending in the longitudinal direction of base 41. Long hole 41a receives shaft 51 projecting from the bottom surface of rotor receiving recess 50 in the thickness direction of frame body 21, whereby shaft 51 is relatively movable with respect to long hole 41a. Thus, base 41 is supported by shaft 51 inserted into long hole 41a to be longitudinally slidable and rotable. The pair of main vanes 42, 43 extend in opposite directions from both longitudinal ends of base 41. The pair of auxiliary vanes 44, 45 are provided in a longitudinal center portion of base 41, and extend in opposite directions from both transverse ends of base 41 along a direction perpendicular to the pair of main vanes 42, 43.
With this configuration, cross-shaped rotor 40 is forced by the flow of the electrolyte solution through slit 35 to rotate while sliding with respect to shaft 51 in a plane perpendicular to the depth direction of slit 35 (i.e. in a plane parallel to the page). Hereinafter, the rotational operation of cross-shaped rotor 40 will be described with reference to
When cross-shaped rotor 40 is in the rotational position shown in
Further, as shown in
Thereafter, cross-shaped rotor 40 reaches the rotational position shown in
The above sequence of rotational movements of cross-shaped rotor 40 is continued as long as cross-shaped rotor 40 remains forced by the flow of the electrolyte solution into rotor receiving recess 50 through electrolyte solution inlet 53. With the sequence of rotational movements, the fluid that has flowed in through electrolyte solution inlet 53 flows out through electrolyte solution outlet 54.
As described above, cross-shaped rotor 40 made of an insulating material that is forced to rotate by the flow of the electrolyte solution, is received in slit 35 of cell frame 20. This allows an increase in the electrical resistance of the electrolyte solution in slit 35, and a reduction in the shunt current loss. Further, since only installation of cross-shaped rotor 40 in slit 35 is required for increasing the electrical resistance of the electrolyte solution, the flow channel structure of cell frame 20 does not become complicated. In addition, there is no need for a complicated mechanism to rotate cross-shaped rotor 40, and therefore a complicated operation control is not needed. For example, to increase the electrical resistance of the electrolyte solution in the slit, the slit may be narrowed or lengthened, which significantly affects the volume of the electrolyte solution flowing through slit 35. The installation of cross-shaped rotor 40 is also advantageous in that it does not have such an adverse effect.
The insulating material of cross-shaped rotor 40 is not limited to a particular one as long as it has a strength sufficient enough not to impair the function of cross-shaped rotor 40, and for example may be the same insulating material as that of frame body 21. As the insulating material of frame body 21, there may be used a material that has an appropriate rigidity, that does not react with an electrolyte solution, and that has resistance to it (chemical resistance, acid resistance, or the like). Such materials include, for example, vinyl chloride, polyethylene, and polypropylene.
The movement of cross-shaped rotor 40 relative to shaft 51 is defined by the shape of rotor receiving recess 50 (i.e. the outline of inner wall surface 52), as can be seen from
Accordingly, the shape of rotor receiving recess 50 as illustrated is merely an example, and may be appropriately changed as long as the above two requirements (i.e. requirement for the direction of rotation of cross-shaped rotor 40 and requirement for blocking the electrical conduction) are met. For example, shaft 51 slides relative to base 41 to reach the end of base 41 (see
The shape of rotor receiving recess 50 also depends on the shape of cross-shaped rotor 40 and the position of shaft 51 relative to slit 35. In other words, once the shape of cross-shaped rotor 40 is determined and the position of shaft 51 relative to slit 35 is determined, the shape of rotor receiving recess 50 may be determined based on them so as to meet the above two requirements. Thus, the shape of cross-shaped rotor 40 is not limited to a particular one as long as it includes base 41, the pair of main vanes 42, 43 and the pair of auxiliary vanes 44, 45. For example, although the shape of rotor receiving recess 50 as illustrated is designed on the assumption that the length of the main vanes 43, 44 and the length of the auxiliary vanes 44, 45 are the same, they may be different. Further, the position of shaft 51 relative to slit 35 is not limited to a particular one as long as it deviates from the straight line connecting electrolyte solution inlet 53 and electrolyte solution outlet 54.
In the above embodiment, cross-shaped rotor 40 is installed at a horizontal portion of slit 35, but the installation position of cross-shaped rotor 40 is not limited thereto. For example, cross-shaped rotor 40 may be installed at a curved portion of slit 35 as shown in
Further, when cell frames 20 are stacked to form cell stack 2, a plurality of cross-shaped rotors 40 corresponding to the same slits 35 may be located at the same position when viewed from the stacking direction. In this case, the plurality of cross-shaped rotors 40 are preferably configured to rotate in synchronization with each other, whereby the flow of the electrolyte solution can be equalized regardless of the position of cell frame 20 (cell 10) to perform stable operation (charge/discharge process). As a method of synchronizing the plurality of cross-shaped rotors 40, there may be used a method of magnetically coupling them to each other, such as by making a part of cross-shaped rotor 40 of a magnetic material.
The shapes of slits 35-38 as illustrated are merely examples and may be other various shapes, and it should be noted that the installation position of cross-shaped rotor 40 may be variously changed depending on the shapes of such slits 35-38. For example,
In the above embodiment, the positive electrolyte solution is supplied from through-hole 31 on the lower left corner to opening 22 so as to flow upward, and then returned to through-hole 32 on the upper right corner, but the flow direction of the positive electrolyte solution is not limited thereto. Similarly, in the above embodiment, the negative electrolyte solution is supplied from through-hole 33 on the lower right corner to opening 21 so as to flow upward, and then returned to through-hole 34 on the upper left corner, but the flow direction of the negative electrolyte solution is not limited thereto. For example, one of the positive and negative electrolyte solutions may flow downward through opening 22. Alternatively, both of the positive and negative electrolyte solutions may flow downward through opening 22. In either case, cross-shaped rotor 40 as described above may be installed in each of slits 35-38.
Further, in the above embodiment, cells 10 are connected to each other such that each of the electrolyte solutions flows in parallel through cells 10, but the connection configuration of cells 10 is not limited thereto. For example, cells 10 may be connected to each other such that each of the electrolyte solutions flows in series through cells 10, and even in such a configuration, cross-shaped rotor 40 as described above may be installed in each of slits 35-38 of cell frame 20. Alternatively, redox flow battery 1 may have a hierarchical flow channel configuration including the combination of parallel and serial flow channels.
In the variation shown in
Further, in addition to or instead of cross-shaped rotor 40 in cell frame 20, connection pipes L11-L14 that respectively connect cell group 7 and pipes L1-L4 may be provided with a rotor received therein and forced to rotate by the flow of the electrolyte solution through connection pipes L11-L14. This also allows, as a whole of redox flow battery 1, an increase in the electrical resistance of the electrolyte solution, and a reduction in the shunt current loss. Such a rotor includes the cross-shaped rotator as described above, a pair of Roots rotors as described below, and a pair of oval gears which operate substantially in the same principle as the Roots rotor.
The hierarchical flow channel configuration of redox flow battery 1 is not limited to the flow channel configuration in which the serial flow channels are connected in parallel as described above, and may be, for example, a flow channel configuration in which parallel flow channels are connected in parallel. That means that cells 10 in each of cell groups 7 may constitute a parallel flow channel similar to that of cells 10 shown in
In the variation shown in
In that case, during the charge process, positive cell 11 is supplied with the positive electrolyte solution containing a relatively large amount of the reduced-state positive-electrode active material from the tank connected to pipe L1, and negative cell 12 is supplied with the negative electrolyte solution containing a relatively large amount of the oxidized-state negative-electrode active material from the tank connected to pipe L3. The oxidation reaction proceeds continuously in positive cell 11, and the positive electrolyte solution containing the positive-electrode active material that has changed into the oxidized state is returned to the tank connected to pipe L2. The reduction reaction proceeds continuously in negative cell 12, and the negative electrolyte solution containing the negative-electrode active material that has changed into the reduced state is returned to the tank connected to pipe L4. On the other hand, during the discharge process, positive cell 11 is supplied with the positive electrolyte solution containing a relatively large amount of the oxidized-state positive-electrode active material from the tank connected to pipe L2, and negative cell 12 is supplied with the negative electrolyte solution containing a relatively large amount of the reduced-state negative-electrode active material from the tank connected to pipe L4. The reduction reaction proceeds continuously in positive cell 11, and the positive electrolyte solution containing the positive-electrode active material that has changed into the reduced state is returned to the tank connected to pipe L1. The oxidation reaction proceeds continuously in negative cell 12, and the negative electrolyte solution containing the negative-electrode active material that has changed into the oxidized state is returned to the tank connected to pipe L3.
In the above embodiment including the variation shown in
In this embodiment, the rotor installed in the slit (and the accompanying rotor receiving recess) are structurally different from those of the first embodiment, and other components are identical to those of the first embodiment. Hereinafter, the components identical to those of the first embodiment will be denoted by identical reference numerals in the drawings, description thereof will be omitted, and only the components that are different from those of the first embodiment will be described. It should be noted that some of the above variations to the first embodiment may also be applied to this embodiment.
In this embodiment, a pair of Roots rotors 61, 62 are received in slit 35. Roots rotors 61, 62 are respectively fixed to rotation shafts 55, 56 that are parallel to the depth direction of slit 35 (i.e. the thickness direction of frame body 21), and each of rotation shafts 55, 56 is rotatably provided in frame body 21. Rotation shafts 55, 56 may be fixed to frame body 21, and Roots rotors 61, 62 may be rotatably mounted to rotation shaft 55, 56, respectively.
Roots rotors 61, 62 are forced by the flow of the electrolyte solution into rotor receiving recess 50 through electrolyte solution inlet 53 to respectively rotate outwardly about rotation shafts 55, 56, i.e., to rotate in opposite directions. In this case, Roots rotors 61, 62 rotate while being substantially in contact with each other. Further, one Roots rotor 61 rotates while being substantially in contact with one portion 52a of inner wall surface 52 of rotor receiving recess 50, and the other Roots rotor 62 rotates while being substantially in contact with the other portion 52b thereof. Thus, Roots rotors 61, 62 can always substantially block the electrical conduction through the electrolyte solution between electrolyte solution inlet 53 and electrolyte solution outlet 54 of rotor receiving recess 50. The term “substantially in contact with” as used herein means that there may be a slight gap between each of Roots rotors 61, 62 and inner wall surface 52 of rotor receiving recess 50, or a slight gap between Roots rotors 61, 62, as long as the electrical conduction through the electrolyte solution occurring at the gap is negligible as described above. The electrolyte solution that has flowed into rotor receiving recess 50 passes through a space formed between each of Roots rotors 61, 62 and inner wall surface 52 of rotor receiving recess 50, and then flows out of rotor receiving recess 50 through electrolyte solution outlet 54.
In the illustrated embodiment, Roots rotors 61, 62 are of the two-lobed type, but may be of the three-lobed type. Further, similar to cross-shaped rotor 40 of the first embodiment, when cell frames 20 are stacked to form cell stack 2, a plurality of pairs of Roots rotors 61, 62 may be located at the same position when viewed from the stacking direction so as to rotate in synchronization with each other. As a method of synchronizing the pairs of Roots rotors 61, 62, there may be used a method by means of mechanical coupling means, such as fixation of the plurality of Roots rotors 61, 62 to common rotation shafts 55, 56, as well as the magnetic coupling means as described above.
Instead of Roots rotors 61, 62, a pair of oval gears which operate in substantially the same principle as the Roots rotors may be used.
Number | Date | Country | Kind |
---|---|---|---|
2018-196652 | Oct 2018 | JP | national |
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/JP2019/040191 | 10/11/2019 | WO | 00 |