Patent Application
20210159532
The present invention relates to a redox flow battery.
One known large capacity storage battery that stores electric power from natural energy generated by solar photovoltaic power generation, wind power generation, etc. is a redox flow battery (RF battery) in PTL 1. The RF battery in PTL 1 includes positive and negative electrodes formed from graphite felt, a membrane interposed between these electrodes, and intermediate films that are disposed on surfaces of the membrane and allow hydrogen ions to pass therethrough.
PTL 1: Japanese Unexamined Patent Application Publication No. 2005-158383
The redox flow battery according to the present disclosure includes:
a membrane; and
electrodes that are disposed in a compressed state on both sides of the membrane and sandwich the membrane,
wherein a thickness x (μm) of the membrane and a compression ratio y (%) of the electrodes satisfy the following relation A or B:
(A) when the electrodes are formed from carbon felt, y<x+60, 30≤y≤85, and 5≤x≤60 hold;
(B) when the electrodes are formed from carbon cloth or carbon paper, y<1.2x+42, 10≤y≤85, and 5≤x≤60 hold, where y={1−(the thickness during compression/the thickness before compression)}×100.
When the intermediate films are provided as described above, direct contact between the electrodes and the membrane can be easily prevented, so that damage such as breakage (puncture) caused by contact (piercing) with the electrodes can be easily prevented even when the membrane is thin. However, it is necessary to provide additional members, e.g., protective members for the membrane such as the intermediate films. This may cause an increase in internal resistance and a reduction in productivity.
Accordingly, it is an object to provide a redox flow battery in which a thin membrane is unlikely to be damaged without providing additional members.
In the present disclosure, the thin membrane is unlikely to be damaged without providing additional members.
The present inventors have conducted extensive studies on how to prevent damage to the membrane caused by contact with the electrodes such as piercing with the electrodes and found that the damage to the membrane can be prevented when the thickness of the membrane and the compression ratio of the electrodes satisfy a specific relation. The present invention is based on this finding. First, embodiments of the present invention will be enumerated and described.
(1) A redox flow battery according to an embodiment of the present invention includes:
a membrane; and
electrodes that are disposed in a compressed state on both sides of the membrane and sandwich the membrane,
wherein a thickness x (μm) of the membrane and a compression ratio y (%) of the electrodes satisfy the following relation A or B:
(A) when the electrodes are formed from carbon felt, y<x+60, 30≤y≤85, and 5≤x≤60 hold;
(B) when the electrodes are formed from carbon cloth or carbon paper, y<1.2x+42, 10≤y≤85, and 5≤x≤60 hold, where y={1−(the thickness during compression/the thickness before compression)}×100.
With the above structure, the thin membrane is unlikely to be damaged without providing additional members. This is because, when any of the above relations holds, an excessive repulsive force of the compressed electrodes does not act on the membrane and contact (piercing) of the membrane with the electrodes can be easily prevented.
Since the thickness x of the membrane is 5 μm or more, the membrane is not excessively thin, and the damage to the membrane caused by contact with the electrodes can be easily prevented. Moreover, the membrane can be easily produced and handled with ease. Since the thickness x of the membrane is 60 μm or less, the membrane is thin, and the internal resistance of the battery can be easily reduced.
Since the lower limit of the compression ratio y is equal to or more than the specified value, the compression ratio is high, and the electrical conductivity of the electrodes can be increased. Therefore, a cell resistivity can be easily reduced. Since the compression ratio y is 85 or less, the electrodes are not compressed excessively, so that the damage to the membrane due to the repulsive force of the electrodes can be easily prevented.
(2) In one aspect of the redox flow battery,
the electrodes may be formed from carbon felt, and
the thickness x (μm) of the membrane may satisfy x≤50.
In this structure, since the thickness of the membrane is smaller, the internal resistance of the battery can be easily reduced.
(3) In one aspect of the redox flow battery including the electrodes formed from carbon felt, the compression ratio y (%) of the electrodes may satisfy 40≤y.
In this structure, since the compression ratio is higher, the electrical conductivity of the electrodes can be increased. Therefore, the cell resistivity can be easily reduced.
(4) In one aspect of the redox flow battery,
the electrodes may be formed from carbon cloth or carbon paper, and
the thickness x (μm) of the membrane may satisfy x≤50.
In this structure, since the thickness of the membrane is smaller, the internal resistance of the battery can be easily reduced.
(5) In one aspect of the redox flow battery including the electrodes formed from carbon cloth or carbon paper,
the compression ratio y (%) of the electrodes may satisfy 20≤y.
In this structure, since the compression ratio is higher, the electrical conductivity of the electrodes can be increased. Therefore, the cell resistivity can be easily reduced.
(6) In one aspect of the redox flow battery,
the electrodes may have a specific gravity of 0.02 g/cm3 or more and 0.5 g/cm3 or less.
When the specific gravity of the electrodes is 0.02 g/cm3 or more, the amount of an electrically conductive component is large, and therefore the internal resistance of the battery can be easily reduced. When the specific gravity of the electrodes is 0.5 g/cm3 or less, the repulsive force of the electrodes is not excessively high, so that the damage to the membrane can be easily prevented.
Details of embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to these exemplary embodiments. The present invention is defined by the scope of the claims and is intended to include any modifications within the scope and meaning equivalent to the scope of the claims. Referring first to
Typically, as shown in
The RF battery 1 includes battery cells 10 each including a positive cell 12 and a negative cell 13 separated from each other by a membrane 11 that allows hydrogen ions to pass therethrough. A positive electrode 14 is installed in the positive cell 12, and the positive electrolyte is circulated through the positive cell 12 by a positive electrolyte circulation mechanism 10P. The positive electrolyte circulation mechanism 10P includes: a positive electrolyte tank 16 that stores the positive electrolyte; a supply pipe 161 and a discharge pipe 162 that connect the positive cell 12 and the positive electrolyte tank 16 to each other; and a pump 163 disposed at an intermediate point in the supply pipe 161. Similarly, a negative electrode 15 is installed in the negative cell 13, and the negative electrolyte is circulated through the negative cell 13 by a negative electrolyte circulation mechanism 10N. The negative electrolyte circulation mechanism 10N includes: a negative electrolyte tank 17 that stores the negative electrolyte; a supply pipe 171 and a discharge pipe 172 that connect the negative cell 13 and the negative electrolyte tank 17 to each other; and a pump 173 disposed at an intermediate point in the supply pipe 171. During charging/discharging operation, the positive and negative electrolytes are circulated through the positive and negative cells 12 and 14 by the pumps 163 and 173. Specifically, the electrolytes flow from the positive and negative electrolyte tanks 16 and 17 through the supply pipes 161 and 171, are supplied to the positive and negative cells 12 and 13, flow from the positive and negative cells 12 and 13 through the discharge pipes 162 and 172, and are discharged to the positive and negative electrolyte tanks 16 and 17. During standby without charging and discharging, the pumps 163 and 173 are stopped, and the positive and negative electrolytes are not circulated.
Generally, the battery cells 10 are formed in a structure called a cell stack 2 shown in
Each cell frame 3 includes a bipolar plate 4 and a frame body 5 that surrounds the outer circumferential edges of the bipolar plate 4, and surfaces of the bipolar plate 4 and an inner circumferential surface of the frame body 5 form recesses 30, the positive electrode 14 (or the negative electrode 15) being disposed in one of the recesses 30. One battery cell 10 is formed between the bipolar plates 4 of cell frames 3 adjacent to each other. The positive electrode 14 (the positive cell 12) of a battery cell 10 and the negative electrode 15 (the negative cell 13) of an adjacent battery cell 10 are disposed on the front and back sides of a bipolar plate 4.
The cell frames 3 include: intermediate cell frames each disposed between adjacent battery cells 10 in one of the layered bodies (
Each frame body 5 supports the corresponding bipolar plate 4 and forms inner regions serving as battery cells 10. The frame body 5 has a rectangular frame shape, and each recess 30 has a rectangular opening shape. The frame body 5 includes: a liquid supply-side piece 51 (the lower side in the drawing sheet of
Liquid supply rectifying portions (not shown) may be formed at an inner circumferential edge of the liquid supply-side piece 51 and used to diffuse the electrolytes flowing through the liquid supply slits 51s along the inner circumferential edge. Liquid discharge rectifying portions (not shown) may be formed at an inner circumferential edge of the liquid discharge-side piece 52. Each liquid discharge rectifying portion is used to correct the electrolyte flowing through the positive electrode 14 (or the negative electrode 15) and supply the electrolyte to the corresponding liquid discharge slit 52s.
The positive and negative electrolytes flow through each cell frame 3 as follows. The positive electrolyte flows from one of the liquid supply manifolds 51m through one of the liquid supply slits 51s that is formed in the liquid supply-side piece 51 and disposed on a first side (the front side in the drawing sheet) of the frame body 5 and is then supplied to the positive electrode 14. Then the positive electrolyte flows from the lower side of the positive electrode 14 toward the upper side as shown by arrows in the upper part of FIG. 3 and is discharged through one of the liquid discharge slits 52s formed in the liquid discharge-side piece 52 to one of the liquid discharge manifolds 52m. The negative electrolyte is supplied and discharged similarly to the positive electrolyte except that the negative electrolyte is supplied and discharged on a second side (the back side in the drawing sheet) of the frame body 5.
A ring-shaped sealing member 6 such as an O-ring or a flat packing is disposed in ring-shaped sealing grooves of adjacent frame bodies 5 to prevent leakage of the electrolytes from a battery cell 10.
Referring to
Each membrane 11 separates the corresponding positive and negative cells 12 and 13 from each other and allows hydrogen ions to pass therethrough between the cells 12 and 13. Each membrane 11 is interposed between the corresponding positive electrode 14 and the corresponding negative electrode 15, fastened by the end plates 22 of the cell stack 2 and the fastening mechanism 23, and sandwiched between the positive electrode 14 and the negative electrode 15. A first side of the membrane 11 is in direct contact with the positive electrode 14, and a second side is in direct contact with the negative electrode 15.
The type of membranes 11 may be an ion-exchange membrane such as a cation-exchange membrane or an anion-exchange membrane. Examples of the material of the membranes 11 include vinyl chloride, fluorine resin, polyethylene, and polypropylene. A well-known material may be used as the material of the membranes 11.
The shape of the membranes 11 may be the same as the outer shape of the cell frames 3 and is a rectangle in this example. The size of the membranes may be the same as the size of the cell frames 3. Passage holes (
The smaller the thickness x of each membrane 11, the better because the internal resistance can be reduced. However, if the thickness x is excessively small, the membrane 11 is easily damaged, e.g., broken, because of contact (piercing) with the positive and negative electrodes 14 and 15, but this depends on the compression ratio y (%) of the positive and negative electrodes 14 and 15. Therefore, the thickness x of the membrane 11 and the compression ratio y (%) of the positive and negative electrodes 14 and 15 may satisfy a specific relation as described later in detail. The thickness x of the membrane 11 is the thickness of a portion sandwiched between the positive electrode 14 and the negative electrode 15 and is the thickness of this portion in the layered bodies assembled but not immersed in the electrolytes.
The electrolytes flow along the positive electrodes 14 and the negative electrodes 15, and a battery reaction thereby proceeds. Examples of the type of positive and negative electrodes 14 and 15 include carbon felt, carbon cloth, and carbon paper that are formed from carbon fibers. Carbon felt is produced by entangling carbon fibers into a felt form using, for example, a needle punching method or a hydroentangling method. Carbon cloth is produced by weaving carbon fibers into a woven fabric having a structure such as a plain weave structure, a sateen weave structure, or a twill weave structure. Carbon paper is a paper-like composite material formed of carbon fibers and carbon and produced, for example, by high-temperature heat treatment.
The positive and negative electrodes 14 and 15 are disposed inside the respective recesses 30 of the cell frames 3. The positive and negative electrodes 14 and 15 each have a rectangular shape conforming to the shape of the recesses 30 of the cell frames 3. The size of the positive and negative electrodes 14 and 15 may be substantially the same as the size of the recesses 30 of the cell frames 3. The thickness of the positive and negative electrodes 14 and 15 depends on their type and the thickness of the uncompressed positive and negative electrodes 14 and 15 before the layered bodies are assembled and is, for example, 0.3 mm or more and 3.0 mm or less. The thickness of each of the positive and negative electrodes 14 and 15 is the thickness of a portion of the each of the positive and negative electrodes 14 and 15 that is sandwiched between a membrane 11 and a bipolar plate 4 and is the thickness of this portion in the layered bodies assembled but not immersed in the electrolytes. The thickness of the uncompressed positive and negative electrodes 14 and 15 before assembly of the layered bodies depends on their type, specific gravity, basis weight, and area. The thickness is, for example, 0.5 mm or more and 5.0 mm or less when the positive and negative electrodes 14 and 15 are formed from carbon felt and is, for example, 0.3 mm or more and 1.0 mm or less when the positive and negative electrodes 14 and 15 are formed from carbon cloth or carbon paper.
The specific gravity of the positive and negative electrodes 14 and 15 may be, for example, 0.02 g/cm3 or more and 0.5 g/cm3 or less and may be 0.05 g/cm3 or more and 0.4 g/cm3 or less. When the specific gravity of the positive and negative electrodes 14 and 15 is 0.02 g/cm3 or more, the internal resistance of the RF battery 1 can be easily reduced because the amount of a conductive component is high. When the specific gravity of the positive and negative electrodes 14 and 15 is 0.5 g/cm3 or less, the repulsive force of the positive and negative electrodes 14 and 15 is not excessively high, so that the damage to the membrane 11 can be easily prevented.
The type of positive and negative electrodes 14 and 15 may be, for example, carbon felt, carbon cloth, or carbon paper as described above, and the relation between the thickness x (μm) of each membrane 11 and the compression ratio y (%) of the positive and negative electrodes 14 and 15 may be appropriately selected mainly according to the type of positive and negative electrodes 14 and 15. The compression ratio y (%) is defined as {1−(the thickness during compression/the thickness before compression)}×100. The thickness during compression is the thickness in the layered bodies assembled but not immersed in the electrolytes. The thickness before compression is the thickness measured according to “JIS L 1913 (2010) Test Methods For Nonwovens” when the electrodes 14 and 15 are formed from carbon felt, is the thickness measured according to “JIS L 1096 (2010) Testing methods for woven and knitted fabrics” when the electrodes 14 and 15 are formed from carbon cloth, and is the thickness measured according to “JIS P 8118 (2014) Paper And Board—Determination Of Thickness, Density And Specific Volume” when the electrodes 14 and 15 are formed from carbon paper. When the positive and negative electrodes 14 and 15 are formed from carbon felt, the thickness of the membrane 11 is denoted by xA, and the compression ratio of the positive and negative electrodes 14 and 15 is denoted by yA. When the positive and negative electrodes 14 and 15 are formed from carbon cloth or carbon paper, the thickness of the membrane 11 is denoted by xB, and the compression ratio of the positive and negative electrodes 14 and 15 is denoted by yB.
(Electrodes Formed from Carbon Felt)
As shown by solid lines in
When the compression ratio yA is 30 or more, the compression ratio of the positive and negative electrodes 14 and 15 is high, and the electrical conductivity of the positive and negative electrodes 14 and 15 can be increased. Therefore, the cell resistivity can be easily reduced. When the compression ratio yA is 85 or less, the positive and negative electrodes 14 and 15 are not compressed excessively, so that the damage to the membrane 11 due to the repulsive force of the electrodes 14 and 15 can be easily prevented. If the positive and negative electrodes 14 and 15 are compressed excessively, the fibers forming the positive and negative electrodes 14 and 15 may be bent, and the repulsive force may be thereby reduced. However, in the above case, the reduction in repulsive force can be prevented. Therefore, even when abnormal operation of the pumps 163 and 173 causes an excessive pressure to act on the membrane 11, the membrane 11 is less likely to be damaged.
When the thickness xA of the membrane 11 is 5 μm or more, the membrane 11 is not excessively thin, and the damage to the membrane 11 caused by contact with the positive and negative electrodes 14 and 15 can be easily prevented. Moreover, the membrane 11 can be easily produced and handled with ease. When the thickness x of the membrane 11 is 60 μm or less, the membrane 11 is thin, and the internal resistance of the RF battery 1 can be easily reduced.
Preferably, the above relation further satisfies yA≤xA+55 (shown by a broken line in
(Electrodes Formed from Carbon Cloth or Carbon Paper)
As shown by solid lines in
The reasons for the upper and lower limits of the compression ratio yB and the reasons for the upper and lower limits of the thickness xB of the membrane are the same as those for the case of carbon felt. The above relation further satisfies preferably yB≤1.2xB+32 (shown by a broken line in
The RF battery 1 in embodiment 1 can be used as a storage battery that is used for the purposes of stabilizing output variations in natural energy power generation such as solar photovoltaic power generation or wind power generation, storing excess electric power generated, and achieving load leveling. The RF battery 1 in embodiment 1 can be used as a storage battery placed in a general power station for the purposes of addressing momentary voltage drop and power failure and achieving load leveling.
In the RF battery 1 according to embodiment 1, the repulsive force of the compressed positive and negative electrodes 14 and 15 that acts on the membranes 11 is not excessively large, and the contact (piercing) of the membranes 11 with the positive and negative electrodes 14 and 15 can be easily prevented. Therefore, the thin membranes 11 are unlikely to be damaged without providing additional members.
Different types of electrodes were prepared. For each type, membranes with different thicknesses x (μm) were used, and different compression ratios y (%) of the positive and negative electrodes were used. The occurrence of piercing of the membrane with the electrodes, the occurrence of breakage of the membrane, and the cell resistivity (Ω·cm2) were evaluated.
Fluorine-based cation-exchange membranes were prepared as the membranes, and two types of electrodes, i.e., carbon felt electrodes and carbon cloth electrodes, were prepared as the positive and negative electrodes. The membranes and the electrodes each have a rectangular shape, and the size of the membranes is the same as the size of the electrodes. The thicknesses of the two types of membranes were changed as shown in Table 1. The specifications of the carbon felt and the carbon cloth are as follows.
Thickness: 2 mm
Specific gravity: 0.13 g/cm3
Thickness: 0.9 mm
Specific gravity: 0.28 g/cm3
The occurrence of piercing was evaluated by measuring a resistance value as follows. Positive and negative electrodes were disposed on the front and back sides of a membrane and pressed from both sides by two copper plates. The thickness of the membrane and the material and compression ratio of the positive and negative electrodes are as shown in Table 1. The compression ratio of the positive and negative electrodes is defined as y={1−(the thickness during compression/the thickness before compression)}×100. This also applies to the evaluation of the occurrence of breakage and the measurement of a cell resistance value described later. Terminals of a commercial tester (CDM-17D manufactured by CUSTOM corporation) were connected to the copper plates to measure the resistance value (Ω) between the terminals. When the resistance value was higher than 100Ω, it was considered that no piercing occurred, and a “Good” rating was assigned. When the resistance value was 100Ω or less, it was considered that piercing occurred, and a “Bad” rating was assigned. The results are shown in Table 1.
Evaluation of the occurrence of breakage was performed using a breakage test jig 100 shown in
A single-cell battery including electrodes with a reaction area of 9 cm2 was produced, and its cell resistivity (Ω·cm2) was measured as follows. The single-cell battery includes a battery element including one positive cell and one negative cell. A positive electrode and a negative electrode were disposed on respective sides of one membrane (ion-exchange membrane) and sandwiched between cell frames each including a bipolar plate. The thickness of the membrane and the material and compression ratio of the positive and negative electrodes areas shown in Table 1. A vanadium sulfate solution (vanadium concentration: 1.7M (mol/L)) was used as the positive and negative electrolytes, and each of the sample single-cell batteries produced was charged and discharged using a constant current with a current density of 70 mA/cm2. In this test, when a preset switching voltage was reached, charging was switched to discharging, and a plurality of charging/discharging cycles were performed. After the charging and discharging, the cell resistivity of each sample was determined. To determine the cell resistivity, the average voltage and average current in one cycle of the plurality of cycles were determined and used as the average voltage/the average current. The results are shown in Table 1. When the cell resistance value was 1.0 Ω·cm2 or less, a “Good” rating was assigned. When the cell resistance value was more than 1.0 Ω·cm2, a “Bad” rating was assigned.
As shown in Table 1, in each of sample Nos. 1-1 to 1-5 and 2-1 to 2-5, no piercing and no breakage were found to occur, and the cell resistivity was found to be low. However, in each of sample Nos. 1-101 to 1-105 and 2-101 to 2-105, at least one of piercing and breakage was found to occur, or the cell resistivity was high although no piercing and no breakage occurred.
The results for sample Nos. 1-1 to 1-5 and 1-101 to 1-105 in which carbon felt was used for the electrodes are shown in
In the case where the carbon felt electrodes are used, a line connecting the point of sample No. 1-102 that is a sample with the highest electrode compression ratio among samples each including the thinnest membrane and the point of sample No. 1-103 that is a sample including the thickest membrane among samples with the highest electrode compression ratio is represented by yA=xA+60 shown by a solid line in
Similarly, in the case where the carbon cloth electrodes are used, a line connecting the point of sample No. 2-102 that is a sample with the highest electrode compression ratio among samples each including the thinnest membrane and the point of sample No. 2-104 that is a sample including the thickest membrane among samples with the highest electrode compression ratio is represented by yB=1.2xB+42 shown by a solid line in
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2017/028897 | 8/9/2017 | WO | 00 |
