JP2018037135A - Redox flow battery operation method, and redox flow battery - Google Patents

Redox flow battery operation method, and redox flow battery Download PDF

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JP2018037135A
JP2018037135A JP2015011849A JP2015011849A JP2018037135A JP 2018037135 A JP2018037135 A JP 2018037135A JP 2015011849 A JP2015011849 A JP 2015011849A JP 2015011849 A JP2015011849 A JP 2015011849A JP 2018037135 A JP2018037135 A JP 2018037135A
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electrolyte
circulation
negative electrode
positive electrode
cell stack
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克也 山西
Katsuya Yamanishi
克也 山西
康充 筒井
Yasumitsu Tsutsui
康充 筒井
貴浩 隈元
Takahiro Kumamoto
貴浩 隈元
敬二 矢野
Keiji Yano
敬二 矢野
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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Priority to PCT/JP2015/085612 priority patent/WO2016117265A1/en
Priority to TW104144255A priority patent/TW201631831A/en
Publication of JP2018037135A publication Critical patent/JP2018037135A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

PROBLEM TO BE SOLVED: To provide a redox flow battery operation method by which one of a pressure of a positive electrode electrolyte and a pressure of a negative electrode electrolyte in a cell stack can be made higher than the other pressure during a period of time from the circulation of the positive and negative electrolytes to the stop of the circulation.SOLUTION: When circulating a positive electrode electrolyte and a negative electrode electrolyte in the cell stack, an amount of circulation of one electrolyte is made larger than an amount of circulation of the other electrolyte, whereby a redox flow battery is put in a pressure difference state in which a pressure of the one electrolyte acting on a diaphragm of a battery cell included in the cell stack is larger than a pressure of the other electrolyte acting on the diaphragm. Also, when reducing amounts of circulation of the positive and negative electrode electrolytes and stopping the circulation of both the electrolytes, an amount of circulation of the one electrolyte is made larger than an amount of circulation of the other electrolyte to maintain the pressure difference state.SELECTED DRAWING: Figure 2

Description

本発明は、瞬時電圧低下対策・停電対策や負荷平準化などに用いられるレドックスフロー電池の運転方法、およびレドックスフロー電池に関するものである。   The present invention relates to a method for operating a redox flow battery used for measures against instantaneous voltage drop, power failure, load leveling, and the like, and a redox flow battery.

太陽光発電や風力発電といった新エネルギーを蓄電する大容量の蓄電池の一つに電解液循環型電池、代表的にはレドックスフロー電池（ＲＦ電池）がある。ＲＦ電池は、正極用電解液に含まれるイオンと負極用電解液に含まれるイオンの酸化還元電位の差を利用して充放電を行う電池である（例えば、特許文献１参照）。図１４のＲＦ電池αの動作原理図に示すように、ＲＦ電池αは、水素イオンを透過させる隔膜１０１で正極部１０２と負極部１０３とに分離された電池セル１００を備える。正極部１０２には正極電極１０４が内蔵され、かつ正極用電解液を貯留する正極用タンク１０６が正極用往路管１０８と正極用復路管１１０を介して接続されている。正極用往路管１０８にはポンプ（正極用送液装置）１１２が設けられており、これら部材１０６，１０８，１１０，１１２によって正極用電解液を循環させる正極用循環機構１００Ｐが構成されている。同様に、負極部１０３には負極電極１０５が内蔵され、かつ負極用電解液を貯留する負極用タンク１０７が負極用往路管１０９と負極用復路管１１１を介して接続されている。負極用往路管１０９にはポンプ（負極用送液装置）１１３が設けられており、これらの部材１０７，１０９，１１１，１１３によって負極用電解液を循環させる負極用循環機構１００Ｎが構成されている。各タンク１０６，１０７に貯留される電解液は、充放電の際にポンプ１１２，１１３によりセル１０２，１０３内に循環される。充放電を行なわない場合、ポンプ１１２，１１３は停止され、電解液は循環されない。   One of large-capacity storage batteries that store new energy such as solar power generation and wind power generation is an electrolyte circulation type battery, typically a redox flow battery (RF battery). An RF battery is a battery that charges and discharges using a difference in redox potential between ions contained in a positive electrode electrolyte and ions contained in a negative electrode electrolyte (see, for example, Patent Document 1). As shown in the operational principle diagram of the RF battery α in FIG. 14, the RF battery α includes a battery cell 100 separated into a positive electrode portion 102 and a negative electrode portion 103 by a diaphragm 101 that allows hydrogen ions to pass therethrough. A positive electrode 104 is built in the positive electrode part 102, and a positive electrode tank 106 for storing a positive electrode electrolyte is connected to the positive electrode forward pipe 108 and the positive electrode return pipe 110. The positive electrode forward pipe 108 is provided with a pump (positive electrode liquid feeding device) 112, and a positive electrode circulation mechanism 100 </ b> P that circulates the positive electrode electrolyte is constituted by these members 106, 108, 110, and 112. Similarly, the negative electrode unit 103 includes a negative electrode 105 therein, and a negative electrode tank 107 that stores a negative electrode electrolyte is connected to the negative electrode forward tube 109 and the negative electrode return tube 111. The negative electrode forward pipe 109 is provided with a pump (negative electrode liquid feeding device) 113, and these members 107, 109, 111, 113 constitute a negative electrode circulation mechanism 100 N that circulates the negative electrode electrolyte. . The electrolyte stored in the tanks 106 and 107 is circulated in the cells 102 and 103 by the pumps 112 and 113 during charging and discharging. When charging / discharging is not performed, the pumps 112 and 113 are stopped and the electrolytic solution is not circulated.

上記電池セル１００は通常、図１５に示すような、セルスタック２００と呼ばれる構造体の内部に複数積層される。セルスタック２００は、サブスタック２００ｓと呼ばれる積層構造物をその両側から二枚のエンドプレート２１０，２２０で挟み込み、締付機構２３０で締め付けることで構成されている（図示する構成では、複数のサブスタック２００ｓを用いている）。サブスタック２００ｓは、図１５の上図に示すように、セルフレーム１２０、正極電極１０４、隔膜１０１、負極電極１０５、およびセルフレーム１２０で構成されるセルユニットを複数積層し、その積層体を給排板１９０，１９０（図１５の下図参照）で挟み込んだ構成を備える。セルユニットに備わるセルフレーム１２０は、貫通窓を有する枠体１２２と貫通窓を塞ぐ双極板１２１とを有しており、双極板１２１の一面側には正極電極１０４が接触するように配置され、双極板１２１の他面側には負極電極１０５が接触するように配置される。この構成では、隣接する各セルフレーム１２０の双極板１２１の間に一つの電池セル１００が形成されることになる。   A plurality of the battery cells 100 are usually stacked inside a structure called a cell stack 200 as shown in FIG. The cell stack 200 is configured by sandwiching a laminated structure called a sub-stack 200 s from both sides with two end plates 210 and 220 and tightening with a tightening mechanism 230 (in the illustrated configuration, a plurality of sub-stacks are arranged). 200 s is used). As shown in the upper diagram of FIG. 15, the sub-stack 200s is formed by stacking a plurality of cell units including the cell frame 120, the positive electrode 104, the diaphragm 101, the negative electrode 105, and the cell frame 120, and supplying the stacked body. It has a configuration sandwiched between the discharge plates 190 and 190 (see the lower diagram of FIG. 15). The cell frame 120 provided in the cell unit includes a frame 122 having a through window and a bipolar plate 121 that closes the through window, and is arranged so that the positive electrode 104 is in contact with one surface side of the bipolar plate 121. The negative electrode 105 is disposed on the other surface side of the bipolar plate 121 so as to be in contact therewith. In this configuration, one battery cell 100 is formed between the bipolar plates 121 of the adjacent cell frames 120.

サブスタック２００ｓにおける給排板１９０，１９０を介した電池セル１００への電解液の流通は、枠体１２２に形成される給液用マニホールド１２３，１２４と、排液用マニホールド１２５，１２６により行われる。正極用電解液は、給液用マニホールド１２３から枠体１２２の一面側（紙面表側）に形成される入口スリットを介して正極電極１０４に供給され、枠体１２２の上部に形成される出口スリットを介して排液用マニホールド１２５に排出される。同様に、負極用電解液は、給液用マニホールド１２４から枠体１２２の他面側（紙面裏側）に形成される入口スリット（点線で示す）を介して負極電極１０５に供給され、枠体１２２の上部に形成される出口スリット（点線で示す）を介して排液用マニホールド１２６に排出される。各セルフレーム１２０間には、Ｏリングや平パッキンなどの環状のシール部材１２７が配置され、サブスタック２００ｓからの電解液の漏れが抑制されている。   Distribution of the electrolyte solution to the battery cell 100 via the supply / discharge plates 190, 190 in the sub stack 200 s is performed by the supply manifolds 123, 124 formed in the frame body 122 and the discharge manifolds 125, 126. . The positive electrode electrolyte is supplied from the liquid supply manifold 123 to the positive electrode 104 through an inlet slit formed on one side (the front side of the paper) of the frame 122, and the outlet slit formed at the top of the frame 122 Then, the liquid is discharged to the drainage manifold 125. Similarly, the negative electrode electrolyte is supplied from the liquid supply manifold 124 to the negative electrode 105 through an inlet slit (shown by a dotted line) formed on the other surface side (back side of the paper surface) of the frame body 122. Is discharged to the drainage manifold 126 through an outlet slit (shown by a dotted line) formed in the upper portion of the liquid. An annular sealing member 127 such as an O-ring or a flat packing is disposed between the cell frames 120, and leakage of the electrolyte from the sub stack 200s is suppressed.

サブスタック２００ｓに備わる電池セル１００と外部機器との間の電力の入出力は、導電性材料で構成された集電板を用いた集電構造によって行われる。集電板は、各サブスタック２００ｓにつき一対設けられており、各集電板はそれぞれ、積層される複数のセルフレーム１２０のうち、積層方向の両端に位置するセルフレーム１２０の双極板１２１に導通されている。   Input / output of electric power between the battery cell 100 provided in the sub stack 200s and an external device is performed by a current collecting structure using a current collecting plate made of a conductive material. A pair of current collecting plates is provided for each sub-stack 200s, and each current collecting plate is electrically connected to the bipolar plate 121 of the cell frame 120 positioned at both ends in the stacking direction among the stacked cell frames 120. Has been.

特開２０１３−８０６１３号公報JP 2013-80613 A

レドックスフロー電池の運用上、セルスタック内の正極電解液の圧力、および負極電解液の圧力のいずれか一方を他方よりも高くしたいというニーズがある。さらに本発明者らの検討によれば、両電解液の循環を停止する際も、一方の電解液の圧力が他方の電解液の圧力よりも高い状態を維持することが好ましいとの知見が得られた。なお、いずれの圧力を高くするかについてはケースバイケースである。   In operation of the redox flow battery, there is a need to make one of the pressure of the positive electrode electrolyte and the pressure of the negative electrode electrolyte in the cell stack higher than the other. Furthermore, according to the study by the present inventors, it was found that it is preferable that the pressure of one electrolyte is maintained higher than the pressure of the other electrolyte even when the circulation of both electrolytes is stopped. It was. Note that which pressure is to be increased is case by case.

本発明は、上記の事情に鑑みてなされたもので、その目的の一つは、正負の電解液の循環から停止までの間、セルスタック内の正極電解液の圧力、および負極電解液の圧力のいずれか一方を他方よりも高くすることができるレドックスフロー電池の運転方法、およびレドックスフロー電池を提供することにある。   The present invention has been made in view of the above circumstances, and one of its purposes is the pressure of the positive electrode electrolyte in the cell stack and the pressure of the negative electrode electrolyte during the period from the circulation of the positive and negative electrolytes to the stop. An object of the present invention is to provide a redox flow battery operating method and a redox flow battery in which any one of the above can be made higher than the other.

本発明の一形態に係るレドックスフロー電池の運転方法は、正極電極、負極電極、および隔膜を有する電池セルを複数積層したセルスタックに、正極用循環機構を用いて正極電解液を循環させると共に、負極用循環機構を用いて負極電解液を循環させるレドックスフロー電池の運転方法である。このレドックスフロー電池の運転方法では、前記正極電解液と前記負極電解液を前記セルスタックに循環させる際、一方の電解液の循環量を他方の電解液の循環量よりも多くして、前記隔膜に作用する前記一方の電解液の圧力を、前記隔膜に作用する前記他方の電解液の圧力よりも大きくした差圧状態とし、前記正極電解液と前記負極電解液の循環量を減少させ、両電解液の循環を停止する際にも、前記一方の電解液の循環量を前記他方の電解液の循環量よりも多くして、前記差圧状態を維持する。   A method for operating a redox flow battery according to an aspect of the present invention is to circulate a positive electrode electrolyte using a positive electrode circulation mechanism in a cell stack in which a plurality of battery cells having a positive electrode, a negative electrode, and a diaphragm are stacked, This is a method for operating a redox flow battery in which a negative electrode electrolyte is circulated using a negative electrode circulation mechanism. In the operating method of the redox flow battery, when the positive electrode electrolyte and the negative electrode electrolyte are circulated through the cell stack, the circulation amount of one electrolyte is larger than the circulation amount of the other electrolyte, The pressure of the one electrolyte acting on the diaphragm is set to a differential pressure state larger than the pressure of the other electrolyte acting on the diaphragm, and the circulation amount of the cathode electrolyte and the anode electrolyte is decreased. Even when the circulation of the electrolytic solution is stopped, the circulating amount of the one electrolytic solution is made larger than the circulating amount of the other electrolytic solution to maintain the differential pressure state.

また、本発明の一形態に係るレドックスフロー電池は、正極電極、負極電極、および隔膜を有する電池セルを複数積層したセルスタックと、前記セルスタックに正極電解液を循環させる正極用循環機構と、前記セルスタックに負極電解液を循環させる負極用循環機構と、を備えるレドックスフロー電池である。このレドックスフロー電池は、前記正極電解液と前記負極電解液の循環から停止までの間、一方の電解液の循環量を他方の電解液の循環量よりも多くなるように、前記正極循環機構と前記負極循環機構とを制御する流量制御部を備える。   A redox flow battery according to an embodiment of the present invention includes a cell stack in which a plurality of battery cells having a positive electrode, a negative electrode, and a diaphragm are stacked, and a positive electrode circulation mechanism that circulates a positive electrode electrolyte in the cell stack; A redox flow battery comprising a negative electrode circulation mechanism for circulating a negative electrode electrolyte in the cell stack. The redox flow battery includes the positive electrode circulation mechanism so that the circulation amount of one electrolyte solution is larger than the circulation amount of the other electrolyte solution from the circulation to the stop of the cathode electrolyte and the anode electrolyte. A flow rate controller for controlling the negative electrode circulation mechanism is provided.

上記レドックスフロー電池の運転方法、およびレドックスフロー電池によれば、正極電解液と負極電解液の循環から停止までの間、セルスタック内の正極電解液の圧力、および負極電解液の圧力のいずれか一方を他方よりも高くすることができる。   According to the above redox flow battery operation method and redox flow battery, either the pressure of the positive electrode electrolyte in the cell stack or the pressure of the negative electrode electrolyte between the circulation and stop of the positive electrode electrolyte and the negative electrode electrolyte One can be higher than the other.

実施形態に係るレドックスフロー電池の概略構成図である。It is a schematic block diagram of the redox flow battery which concerns on embodiment. 正極電解液と負極電解液の循環を停止する制御パターンＩに係るグラフである。It is a graph which concerns on the control pattern I which stops the circulation of a positive electrode electrolyte and a negative electrode electrolyte. 正極電解液と負極電解液の循環を停止する制御パターンＩＩに係るグラフである。It is a graph which concerns on the control pattern II which stops the circulation of a positive electrode electrolyte and a negative electrode electrolyte. 正極用復路管を負極用復路管よりも長くすることで構成した差圧形成機構の概略構成図である。It is a schematic block diagram of the differential pressure formation mechanism comprised by making the return pipe for positive electrodes longer than the return pipe for negative electrodes. 正極用復路管を負極用復路管よりも細くすることで構成した差圧形成機構の概略構成図である。It is a schematic block diagram of the differential pressure formation mechanism comprised by making the return pipe for positive electrodes thinner than the return pipe for negative electrodes. 正極用復路管を負極用復路管よりも屈曲させることで構成した差圧形成機構の概略構成図である。It is a schematic block diagram of the differential pressure formation mechanism comprised by bending the return pipe for positive electrodes rather than the return pipe for negative electrodes. 正極用熱交換器と負極用熱交換器とで構成した差圧形成機構の概略構成図である。It is a schematic block diagram of the differential pressure | voltage formation mechanism comprised with the heat exchanger for positive electrodes, and the heat exchanger for negative electrodes. 正極電解液と負極電解液の循環を停止する制御パターンＩＩＩに係るグラフである。It is a graph which concerns on the control pattern III which stops the circulation of a positive electrode electrolyte and a negative electrode electrolyte. 正極電解液と負極電解液の循環を停止する制御パターンＩＶに係るグラフである。It is a graph which concerns on the control pattern IV which stops the circulation of a positive electrode electrolyte and a negative electrode electrolyte. 負極用復路管を正極用復路管よりも長くすることで構成した差圧形成機構の概略構成図である。It is a schematic block diagram of the differential pressure formation mechanism comprised by making the return pipe for negative electrodes longer than the return pipe for positive electrodes. 負極用復路管を正極用復路管よりも細くすることで構成した差圧形成機構の概略構成図である。It is a schematic block diagram of the differential pressure formation mechanism comprised by making the return pipe for negative electrodes thinner than the return pipe for positive electrodes. 負極用復路管を正極用復路管よりも屈曲させることで構成した差圧形成機構の概略構成図である。It is a schematic block diagram of the differential pressure formation mechanism comprised by bending the return pipe for negative electrodes rather than the return pipe for positive electrodes. 正極用熱交換器と負極用熱交換器とで構成した差圧形成機構の概略構成図である。It is a schematic block diagram of the differential pressure | voltage formation mechanism comprised with the heat exchanger for positive electrodes, and the heat exchanger for negative electrodes. レドックスフロー電池の動作原理図である。It is an operation | movement principle figure of a redox flow battery. セルスタックの概略構成図である。It is a schematic block diagram of a cell stack.

［本発明の実施形態の説明］
最初に本発明の実施形態の内容を列記して説明する。 [Description of Embodiment of the Present Invention]
First, the contents of the embodiment of the present invention will be listed and described.

＜１＞実施形態に係るレドックスフロー電池の運転方法は、正極電極、負極電極、および隔膜を有する電池セルを複数積層したセルスタックに、正極用循環機構を用いて正極電解液を循環させると共に、負極用循環機構を用いて負極電解液を循環させるレドックスフロー電池の運転方法である。このレドックスフロー電池の運転方法では、前記正極電解液と前記負極電解液を前記セルスタックに循環させる際、一方の電解液の循環量を他方の電解液の循環量よりも多くして、前記隔膜に作用する前記一方の電解液の圧力を、前記隔膜に作用する前記他方の電解液の圧力よりも大きくした差圧状態とし、前記正極電解液と前記負極電解液の循環量を減少させ、両電解液の循環を停止する際にも、前記一方の電解液の循環量を前記他方の電解液の循環量よりも多くして、前記差圧状態を維持する。 <1> The operation method of the redox flow battery according to the embodiment circulates the positive electrode electrolyte using a positive electrode circulation mechanism in a cell stack in which a plurality of battery cells each having a positive electrode, a negative electrode, and a diaphragm are stacked. This is a method for operating a redox flow battery in which a negative electrode electrolyte is circulated using a negative electrode circulation mechanism. In the operating method of the redox flow battery, when the positive electrode electrolyte and the negative electrode electrolyte are circulated through the cell stack, the circulation amount of one electrolyte is larger than the circulation amount of the other electrolyte, The pressure of the one electrolyte acting on the diaphragm is set to a differential pressure state larger than the pressure of the other electrolyte acting on the diaphragm, and the circulation amount of the cathode electrolyte and the anode electrolyte is decreased. Even when the circulation of the electrolytic solution is stopped, the circulating amount of the one electrolytic solution is made larger than the circulating amount of the other electrolytic solution to maintain the differential pressure state.

セルスタック内の正極電解液の圧力、および負極電解液の圧力のいずれか一方を他方よりも高くすると、セルスタック内の隔膜に作用する一方の電解液の圧力が、隔膜に作用する他方の電解液の圧力よりも大きい差圧状態となる。本発明者らの検討によれば、両電解液を循環させる際に上記差圧状態を維持する場合、両電解液の循環を停止する際にも、上記差圧状態を維持しておくことが好ましいとの知見が得られた。両電解液の循環の停止の際に隔膜に作用する圧力の方向が変わると、隔膜に過剰な負荷がかかる恐れがあるからである。   When either the pressure of the positive electrode electrolyte in the cell stack or the pressure of the negative electrode electrolyte is higher than the other, the pressure of the one electrolyte acting on the diaphragm in the cell stack becomes the other electrolyte acting on the diaphragm. The differential pressure state is greater than the liquid pressure. According to the study by the present inventors, when the above-mentioned differential pressure state is maintained when both electrolytic solutions are circulated, the above-mentioned differential pressure state can be maintained even when the circulation of both electrolytic solutions is stopped. The knowledge that it was preferable was obtained. This is because if the direction of the pressure acting on the diaphragm changes when the circulation of both electrolytes is stopped, an excessive load may be applied to the diaphragm.

本発明者らの知見に基づく上記レドックスフロー電池の運転方法によれば、セルスタック内に正極電解液と負極電解液の循環をさせるときも、両電解液の循環を停止するときも、上記差圧状態を維持しているため、隔膜に作用する圧力の方向を一定にすることができる。その結果、隔膜に過剰な応力が作用することを抑制することができ、隔膜の損傷を防止することができる。   According to the operation method of the above redox flow battery based on the knowledge of the present inventors, the difference between the positive electrode solution and the negative electrode electrolyte is circulated in the cell stack and the circulation of both the electrolytes is stopped. Since the pressure state is maintained, the direction of the pressure acting on the diaphragm can be made constant. As a result, it is possible to suppress excessive stress from acting on the diaphragm, and to prevent the diaphragm from being damaged.

＜２＞実施形態に係るレドックスフロー電池の運転方法として、前記正極電解液と前記負極電解液の循環を停止する際、前記一方の電解液の循環量の減少速度を、前記他方の電解液の循環量の減少速度よりも大きくし、両電解液の循環を同時に停止する形態を挙げることができる。 <2> As a method for operating the redox flow battery according to the embodiment, when the circulation of the positive electrode electrolyte and the negative electrode electrolyte is stopped, the rate of decrease in the circulation amount of the one electrolyte is changed to that of the other electrolyte. It is possible to use a mode in which the circulation rate of the both electrolytes is stopped simultaneously by increasing the rate of circulation rate reduction.

上記形態のように、一方の電解液の循環量が他方の電解液の循環量よりも多い状態を維持した上で、一方の電解液の循環量の減少速度を、他方の電解液の循環量の減少速度より大きくすることで、両電解液の循環量の差を徐々に小さくしながら両電解液の循環を停止することができる。その結果、両電解液の循環を停止するまでの間、隔膜に作用する応力を徐々に小さくすることができるため、隔膜の損傷を効果的に防止することができる。   While maintaining the state where the circulation amount of one electrolyte solution is larger than the circulation amount of the other electrolyte solution as in the above embodiment, the decrease rate of the circulation amount of one electrolyte solution is set to the circulation amount of the other electrolyte solution. By making it larger than the decrease rate of, the circulation of both electrolytes can be stopped while gradually reducing the difference in the circulation amount of both electrolytes. As a result, since the stress acting on the diaphragm can be gradually reduced until the circulation of both electrolytes is stopped, damage to the diaphragm can be effectively prevented.

＜３＞実施形態に係るレドックスフロー電池の運転方法として、前記正極電解液と前記負極電解液の循環を停止する際、前記一方の電解液の循環量の減少速度と、前記他方の電解液の循環量の減少速度と、を調整し、前記一方の電解液の循環を、前記他方の電解液の循環よりも後に停止する形態を挙げることができる。 <3> As a method for operating the redox flow battery according to the embodiment, when the circulation of the positive electrode electrolyte and the negative electrode electrolyte is stopped, the rate of decrease in the circulation amount of the one electrolyte solution, A mode in which the rate of decrease in the circulation amount is adjusted and the circulation of the one electrolyte solution is stopped after the circulation of the other electrolyte solution can be exemplified.

上記形態に示すように、一方の電解液の循環を、他方の電解液の循環よりも後に停止することで、両電解液の循環が停止する瞬間まで、確実に上記差圧状態を維持することができる。   As shown in the above embodiment, by stopping the circulation of one electrolytic solution after the circulation of the other electrolytic solution, the above differential pressure state is reliably maintained until the moment when the circulation of both electrolytic solutions is stopped. Can do.

＜４＞実施形態に係るレドックスフロー電池の運転方法として、前記一方の電解液を循環させる循環機構に備わる電解液のタンクを、前記他方の電解液を循環させる循環機構に備わる電解液のタンクよりも高い位置に配置し、両電解液が循環していないときに、前記セルスタック内に両電解液を満たしたままとする形態を挙げることができる。 <4> As an operating method of the redox flow battery according to the embodiment, an electrolytic solution tank provided in a circulation mechanism for circulating the one electrolytic solution is used as an electrolytic solution tank provided in a circulation mechanism for circulating the other electrolytic solution. The cell stack may be filled with both electrolytes when both electrolytes are not circulated.

上記形態によれば、両電解液が循環していないときにも、上記差圧状態を維持することができる。また、両電解液が循環していないときに差圧状態が維持されていれば、両電解液の循環を再開する際、一方の電解液を循環させる装置（例えば、ポンプなどの送液装置）の始動が何らかの理由で他方の電解液を循環させる装置の始動より遅れるなどしても、隔膜に作用する他方の電解液の圧力が一方の電解液の圧力よりも高くなる逆差圧状態となり難い。   According to the said form, even when both electrolyte solution is not circulating, the said differential pressure state can be maintained. Also, if the differential pressure state is maintained when both electrolytes are not circulating, a device that circulates one electrolyte solution (for example, a liquid delivery device such as a pump) when recirculation of both electrolyte solutions is resumed. Even if the start-up is delayed from the start-up of the device that circulates the other electrolyte for some reason, it is difficult to achieve a reverse differential pressure state in which the pressure of the other electrolyte acting on the diaphragm is higher than the pressure of the one electrolyte.

＜５＞実施形態に係るレドックスフロー電池は、正極電極、負極電極、および隔膜を有する電池セルを複数積層したセルスタックと、前記セルスタックに正極電解液を循環させる正極用循環機構と、前記セルスタックに負極電解液を循環させる負極用循環機構と、を備えるレドックスフロー電池である。このレドックスフロー電池は、前記正極電解液と前記負極電解液の循環から停止までの間、一方の電解液の循環量を他方の電解液の循環量よりも多くなるように、前記正極循環機構と前記負極循環機構とを制御する流量制御部を備える。 <5> A redox flow battery according to an embodiment includes a cell stack in which a plurality of battery cells each having a positive electrode, a negative electrode, and a diaphragm, a positive electrode circulation mechanism for circulating a positive electrolyte in the cell stack, and the cell A redox flow battery comprising: a negative electrode circulation mechanism that circulates a negative electrode electrolyte in a stack. The redox flow battery includes the positive electrode circulation mechanism so that the circulation amount of one electrolyte solution is larger than the circulation amount of the other electrolyte solution from the circulation to the stop of the cathode electrolyte and the anode electrolyte. A flow rate controller for controlling the negative electrode circulation mechanism is provided.

上記レドックスフロー電池によれば、セルスタック内に正極電解液と負極電解液の循環をさせるときにも、両電解液の循環を停止するときにも、上記差圧状態を維持することができる。そのため、上記レドックスフロー電池は、レドックスフロー電池に備わる隔膜に作用する圧力の方向が一定で、隔膜が損傷し難いレドックスフロー電池となる。   According to the redox flow battery, the differential pressure state can be maintained both when the positive and negative electrolytes are circulated in the cell stack and when the circulation of both electrolytes is stopped. Therefore, the redox flow battery is a redox flow battery in which the direction of pressure acting on the diaphragm provided in the redox flow battery is constant and the diaphragm is not easily damaged.

［本発明の実施形態の詳細］
以下、実施形態に係るレドックスフロー電池（ＲＦ電池）の運転方法、およびＲＦ電池の実施形態を説明する。実施形態において、同一の符号で示される部材は、同一の機能を備える。なお、本発明は実施形態に示される構成に限定されるわけではなく、特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内の全ての変更が含まれることを意図する。 [Details of the embodiment of the present invention]
Hereinafter, the operation method of the redox flow battery (RF battery) according to the embodiment and the embodiment of the RF battery will be described. In the embodiment, members indicated by the same reference numerals have the same function. In addition, this invention is not necessarily limited to the structure shown by embodiment, and is shown by the claim, and intends that all the changes within the meaning and range equivalent to a claim are included.

＜実施形態１＞
≪ＲＦ電池の全体構成≫
図１の概略図に示すように、本実施形態に係るＲＦ電池１は、従来のＲＦ電池と同様に、セルスタック２と、正極用循環機構３Ｐと、負極用循環機構３Ｎと、を備える。この図１では、セルスタック２の構成を簡素化して示しているが、実際には図１５の下図を参照して説明したように、複数のサブスタック２００ｓをエンドプレート２１０，２２０で締め付けた構成を備えている。また、図１のセルスタック２には、電池セル１００を一つだけ図示しているが、実際には複数の電池セル１００が積層されている。各電池セル１００は、正極電極１０４と、負極電極１０５と、両電極１０４，１０５を隔てる隔膜１０１と、で構成される。 <Embodiment 1>
≪Overall configuration of RF battery≫
As shown in the schematic diagram of FIG. 1, the RF battery 1 according to the present embodiment includes a cell stack 2, a positive electrode circulation mechanism 3P, and a negative electrode circulation mechanism 3N, as in the conventional RF battery. In FIG. 1, the configuration of the cell stack 2 is shown in a simplified manner, but actually, a configuration in which a plurality of sub-stacks 200 s are fastened with end plates 210 and 220 as described with reference to the lower diagram of FIG. 15. It has. Moreover, although only one battery cell 100 is illustrated in the cell stack 2 of FIG. 1, a plurality of battery cells 100 are actually stacked. Each battery cell 100 includes a positive electrode 104, a negative electrode 105, and a diaphragm 101 that separates both electrodes 104 and 105.

正極用循環機構３Ｐは、正極用タンク１０６と、正極用往路管１０８および正極用復路管１１０で構成される正極用管路と、ポンプ（正極用送液装置）１１２と、を備える。正極用往路管１０８は、正極用タンク１０６からセルスタック２に正極電解液を供給する配管であり、正極用復路管１１０はセルスタック２から正極用タンク１０６に正極電解液を排出する配管である。ポンプ１１２は、正極用往路管１０８の途中に設けられ、正極電解液をセルスタック２に送り出す部材である。このような構成の場合、正極電解液の循環量は、ポンプ１１２の出力を調節することで変化させることができる。   The positive electrode circulation mechanism 3 </ b> P includes a positive electrode tank 106, a positive electrode pipe constituted by the positive electrode forward pipe 108 and the positive electrode return pipe 110, and a pump (liquid supply device for positive electrode) 112. The positive electrode forward pipe 108 is a pipe that supplies the positive electrode electrolyte from the positive electrode tank 106 to the cell stack 2, and the positive electrode return pipe 110 is a pipe that discharges the positive electrode electrolyte from the cell stack 2 to the positive electrode tank 106. . The pump 112 is a member that is provided in the middle of the positive electrode outward pipe 108 and that sends out the positive electrode electrolyte to the cell stack 2. In the case of such a configuration, the circulation amount of the positive electrode electrolyte can be changed by adjusting the output of the pump 112.

負極用循環機構３Ｎは、負極用タンク１０７と、負極用往路管１０９および負極用復路管１１１で構成される負極用管路と、ポンプ（負極用送液装置）１１３と、を備える。負極用往路管１０９は、負極用タンク１０７からセルスタック２に負極電解液を供給する配管であり、負極用復路管１１１はセルスタック２から負極用タンク１０７に負極電解液を排出する配管である。ポンプ１１３は、負極用往路管１０９の途中に設けられ、負極電解液をセルスタック２に送り出す部材である。このような構成の場合、負極電解液の循環量は、ポンプ１１３の出力を調整することで変化させることができる。   The negative electrode circulation mechanism 3 </ b> N includes a negative electrode tank 107, a negative electrode conduit composed of a negative electrode outward passage 109 and a negative electrode return conduit 111, and a pump (negative electrode liquid feeding device) 113. The negative electrode forward pipe 109 is a pipe for supplying a negative electrode electrolyte from the negative electrode tank 107 to the cell stack 2, and the negative electrode return pipe 111 is a pipe for discharging the negative electrode electrolyte from the cell stack 2 to the negative electrode tank 107. . The pump 113 is a member that is provided in the middle of the negative electrode outgoing pipe 109 and that feeds the negative electrode electrolyte solution to the cell stack 2. In the case of such a configuration, the circulation amount of the negative electrode electrolyte can be changed by adjusting the output of the pump 113.

上記構成を備える実施形態のＲＦ電池１における従来との主な相違点は、セルスタック２内に正極電解液と負極電解液を循環させるときにも、両電解液の循環を停止するときにも、隔膜１０１に作用する正極電解液の圧力が負極電解液の圧力よりも大きい第一の差圧状態（塗り潰し矢印の方向に圧力が作用する状態）を維持するための流量制御部５を備えることである。   The main difference between the RF battery 1 of the embodiment having the above-described configuration and the conventional one is that the positive electrode electrolyte and the negative electrode electrolyte are circulated in the cell stack 2 and the circulation of both electrolytes is stopped. And a flow rate controller 5 for maintaining a first differential pressure state (a state in which the pressure acts in the direction of the filled arrow) in which the pressure of the positive electrode electrolyte acting on the diaphragm 101 is larger than the pressure of the negative electrode electrolyte. It is.

≪流量制御部≫
流量制御部５は、ポンプ（正極用送液装置）１１２の出力と、ポンプ（負極用送液装置）１１３の出力と、を相対的に制御するように、両ポンプ１１２，１１３に電気的に接続される。各ポンプ１１２，１１３による電解液の送液量（即ち、電解液の循環量）は、ポンプ１１２，１１３の出力に応じて変化する。本実施形態の場合、ポンプ１１２からの正極電解液の送液量を、ポンプ１１３からの負極電解液の送液量よりも大きくすることで、セルスタック２内の隔膜１０１に作用する正極電解液の圧力が負極電解液の圧力よりも大きい第一の差圧状態を作り出している。 ≪Flow control part≫
The flow rate controller 5 is electrically connected to both the pumps 112 and 113 so as to relatively control the output of the pump (liquid feeding device for positive electrode) 112 and the output of the pump (liquid feeding device for negative electrode) 113. Connected. The amount of electrolyte sent by each pump 112, 113 (that is, the amount of electrolyte circulated) varies according to the output of the pumps 112, 113. In the case of the present embodiment, the positive electrode electrolyte that acts on the diaphragm 101 in the cell stack 2 by making the amount of the positive electrode electrolyte sent from the pump 112 larger than the amount of the negative electrode electrolyte sent from the pump 113. Creates a first differential pressure state in which the pressure of is greater than the pressure of the negative electrode electrolyte.

流量制御部５は、両電解液の循環を停止する際にも、上記第一の差圧状態を維持できるように、ポンプ１１２，１１３を制御する。代表的な二つの制御パターンを図２、図３に基づいて説明する。図２，３はいずれも、両電解液を循環させた状態から循環を停止させるまでの間のポンプ１１２，１１３からの送液量（即ち、両電解液の循環量）の変化を示すグラフである。図２，３のグラフの縦軸は、ポンプ１１２，１１３からの送液量、横軸は時間である。また、グラフ中の実線は正極電解液の送液量、点線は負極電解液の送液量を示す。   The flow control unit 5 controls the pumps 112 and 113 so that the first differential pressure state can be maintained even when the circulation of both electrolytes is stopped. Two typical control patterns will be described with reference to FIGS. 2 and 3 are graphs showing changes in the amount of liquid fed from the pumps 112 and 113 (that is, the amount of circulation of both electrolytes) from the state in which both electrolytes are circulated until the circulation is stopped. is there. 2 and 3, the vertical axis represents the amount of liquid fed from the pumps 112 and 113, and the horizontal axis represents time. Further, the solid line in the graph indicates the amount of the positive electrode electrolyte supplied, and the dotted line indicates the amount of the negative electrode electrolyte supplied.

［制御パターンＩ］
図２のグラフに示すように、制御パターンＩでは、正極電解液の送液量を負極電解液の送液量よりも大きくして両電解液を循環させた状態から、時刻ｔ０で両電解液の循環を停止し始める。その際、正極電解液の送液量（循環量）の減少速度を、負極電解液の送液量（循環量）の減少速度よりも大きくしている。そして、時刻ｔ１で両電解液の送液をほぼ同時に停止する。 [Control pattern I]
As shown in the graph of FIG. 2, in the control pattern I, both electrolyte solutions are supplied at a time t0 from the state in which both electrolyte solutions are circulated with the amount of cathode electrolyte supplied larger than the amount of anode electrolyte supplied. Start to stop circulating. At this time, the rate of decrease in the amount (circulation amount) of the positive electrode electrolyte is set to be greater than the rate of decrease in the amount (circulation amount) of the negative electrode electrolyte. At time t1, the feeding of both electrolytes is stopped almost simultaneously.

上記制御パターンＩによれば、両電解液の送液量（循環量）の差を徐々に小さくしながら両電解液の循環を停止することができる。その結果、両電解液の循環を停止するまでの間、隔膜１０１（図１参照）に作用する応力を徐々に小さくすることができるため、隔膜１０１の損傷を効果的に防止することができる。   According to the control pattern I, it is possible to stop the circulation of both electrolytic solutions while gradually reducing the difference in the amount (circulation amount) of both electrolytic solutions. As a result, since the stress acting on the diaphragm 101 (see FIG. 1) can be gradually reduced until the circulation of both electrolytes is stopped, damage to the diaphragm 101 can be effectively prevented.

［制御パターンＩＩ］
図３のグラフに示すように、制御パターンＩＩでも、時刻ｔ０で両電解液の循環を停止し始める。ここで、制御パターンＩＩでは、正極電解液の送液量（循環量）の減少速度と、負極電解液の送液量（循環量）の減少速度と、を同程度としている。もともと、負極電解液の送液量が正極電解液の送液量よりも小さかったために、両電解液の送液量の減少速度が同程度であると、時刻ｔ２で負極電解液の送液が停止し、その後、時刻ｔ３で正極電解液の送液が停止する。つまり、負極電解液の循環が停止した後も正極電解液がセルスタック２（図１参照）内を循環することになるため、両電解液の循環が停止する瞬間まで、確実に第一の差圧状態を維持することができる。 [Control Pattern II]
As shown in the graph of FIG. 3, also in the control pattern II, the circulation of both electrolytes starts to be stopped at time t0. Here, in the control pattern II, the rate of decrease in the amount (circulation amount) of the positive electrode electrolyte is substantially equal to the rate of decrease in the amount (circulation amount) of the negative electrode electrolyte. Originally, since the amount of the negative electrode electrolyte supplied was smaller than the amount of the positive electrode electrolyte supplied, when the rate of decrease in the amount of both electrolytes supplied was the same, the negative electrode electrolyte was supplied at time t2. After that, the feeding of the positive electrode electrolyte stops at time t3. That is, since the cathode electrolyte circulates in the cell stack 2 (see FIG. 1) even after the circulation of the anode electrolyte is stopped, the first difference is surely made until the moment when the circulation of both electrolytes is stopped. The pressure state can be maintained.

なお、図１に示すＲＦ電池１の正極用管路と負極用管路にはそれぞれ、図示しない複数のバルブが存在する。それらバルブの開度・開閉回数を流量制御部５に制御させても構わない。そうすることで、上記二つの制御パターンを行い易くなる。   A plurality of valves (not shown) exist in each of the positive electrode conduit and the negative electrode conduit of the RF battery 1 shown in FIG. You may make the flow control part 5 control the opening degree and the frequency | count of opening / closing of these valves. By doing so, it becomes easy to perform the two control patterns.

≪循環停止時に係る構成≫
図１に示す上記流量制御部５の制御によって両電解液の循環を停止した後も、隔膜１０１に作用する正極電解液の圧力が負極電解液の圧力よりも大きい第一の差圧状態を維持することが好ましい。両電解液が循環していないときに差圧状態が維持されていれば、両電解液の循環を再開する際、正極電解液を循環させるポンプ１１２の始動が何らかの理由で負極電解液を循環させるポンプ１１３の始動より遅れるなどしても、隔膜１０１に作用する負極電解液の圧力が正極電解液の圧力よりも高くなる逆差圧状態となり難いからである。 ≪Configuration related to circulation stop≫
Even after the circulation of both electrolytes is stopped by the control of the flow rate control unit 5 shown in FIG. 1, the first differential pressure state in which the pressure of the positive electrode electrolyte acting on the diaphragm 101 is larger than the pressure of the negative electrode electrolyte is maintained. It is preferable to do. If the differential pressure state is maintained when both electrolytes are not circulated, when the circulation of both electrolytes is resumed, the start of the pump 112 that circulates the cathode electrolyte causes the anode electrolyte to circulate for some reason. This is because even if it is delayed from the start of the pump 113, it is difficult to achieve a reverse differential pressure state in which the pressure of the negative electrode electrolyte acting on the diaphragm 101 is higher than the pressure of the positive electrode electrolyte.

両電解液の循環が循環していないときに上記第一の差圧状態を維持するには、例えば正極用タンク１０６を負極用タンク１０７よりも高い位置に配置すると良い。そして、両電解液の循環を停止した後も、セルスタック２内に両電解液を満たしたままとしておく。そうすることで、両電解液が循環していなくても、位置エネルギーによって第一の差圧状態を維持することができる。   In order to maintain the first differential pressure state when both the electrolytes are not circulated, for example, the positive electrode tank 106 may be disposed at a higher position than the negative electrode tank 107. Then, even after the circulation of both electrolytes is stopped, the cell stack 2 is filled with both electrolytes. By doing so, even if both electrolytes are not circulating, the first differential pressure state can be maintained by the potential energy.

≪第一の差圧状態を形成し易くするための構成≫
上記ポンプ１１２，１１３からの送液量の差に加えて、第一の差圧状態を形成し易くするための第一の差圧形成機構をＲＦ電池１に設けても良い。第一の差圧形成機構は、ＲＦ電池１に備わる既存の部材の構成（主として寸法）を変えること、具体的には正極用循環機構３Ｐと負極用循環機構３Ｎとに構成上の差異を設けることで形成することができる。以下、第一の差圧形成機構の一形態を図４〜図７に基づいて説明する。図４〜図６ではタンク及びポンプを省略し、図７ではさらにセルスタックも省略している。 ≪Configuration to facilitate the formation of the first differential pressure state≫
In addition to the difference in the amount of liquid fed from the pumps 112 and 113, the RF battery 1 may be provided with a first differential pressure forming mechanism for facilitating the formation of the first differential pressure state. The first differential pressure forming mechanism changes the configuration (mainly dimensions) of the existing members provided in the RF battery 1, and specifically provides a structural difference between the positive electrode circulation mechanism 3P and the negative electrode circulation mechanism 3N. Can be formed. Hereinafter, an embodiment of the first differential pressure forming mechanism will be described with reference to FIGS. 4 to 6, the tank and the pump are omitted, and the cell stack is also omitted in FIG.

［正負の管路の長さを変える］
図４には、正極用復路管１１０を、負極用復路管１１１よりも長くすることで形成した差圧形成機構６Ａが示されている。管を長くすると、管内を流れる電解液の圧力損失が増大する。図４の場合は、正極用復路管１１０を負極用復路管１１１よりも長くしているので、正極用復路管１１０の圧力損失が負極用復路管１１１の圧力損失よりも大きくなる。その結果、セルスタック２内の正極電解液の圧力が負極電解液の圧力よりも高くなり、セルスタック２内の隔膜１０１に作用する正極電解液の圧力が負極電解液の圧力よりも大きい第一の差圧状態を作り出すことができる。 [Change the length of the positive and negative pipelines]
FIG. 4 shows a differential pressure forming mechanism 6 </ b> A formed by making the positive return pipe 110 longer than the negative return pipe 111. When the tube is lengthened, the pressure loss of the electrolyte flowing in the tube increases. In the case of FIG. 4, the positive return pipe 110 is longer than the negative return pipe 111, so that the pressure loss of the positive return pipe 110 is larger than the pressure loss of the negative return pipe 111. As a result, the pressure of the positive electrode electrolyte in the cell stack 2 becomes higher than the pressure of the negative electrode electrolyte, and the pressure of the positive electrode electrolyte acting on the diaphragm 101 in the cell stack 2 is larger than the pressure of the negative electrode electrolyte. The differential pressure state can be created.

図示しないが、負極用往路管１０９を、正極用往路管１０８よりも長くすることで、差圧形成機構６Ａを形成しても構わない。この場合、セルスタック２内の負極電解液の圧力が低くなり、相対的に正極電解液の圧力が負極電解液の圧力よりも大きい状態が作り出される。もちろん、復路管１１０，１１１の長さを変える構成と、往路管１０８，１０９の長さを変える構成と、を組み合わせて差圧形成機構６Ａを形成することもできる。   Although not shown, the differential pressure forming mechanism 6 </ b> A may be formed by making the negative electrode outward tube 109 longer than the positive electrode outward tube 108. In this case, the pressure of the negative electrode electrolyte in the cell stack 2 is reduced, and a state in which the pressure of the positive electrode electrolyte is relatively larger than the pressure of the negative electrode electrolyte is created. Of course, the differential pressure forming mechanism 6A can be formed by combining the configuration in which the lengths of the return pipes 110 and 111 are changed and the configuration in which the lengths of the outgoing pipes 108 and 109 are changed.

［正負の管路の太さを変える］
図５には、正極用復路管１１０を、負極用復路管１１１よりも細くすることで形成した差圧形成機構６Ｂが示されている。管を細くすると、管内を流れる電解液の圧力損失が増大する。図５の場合は、正極用復路管１１０を負極用復路管１１１よりも細くしているので、正極用復路管１１０の圧力損失が負極用復路管１１１の圧力損失よりも大きくなる。その結果、セルスタック２内の正極電解液の圧力が負極電解液の圧力よりも高くなり、セルスタック２内の隔膜１０１に作用する正極電解液の圧力が負極電解液の圧力よりも大きい第一の差圧状態を作り出すことができる。 [Change thickness of positive and negative pipe lines]
FIG. 5 shows a differential pressure forming mechanism 6B formed by making the positive return pipe 110 thinner than the negative return pipe 111. When the tube is made thinner, the pressure loss of the electrolyte flowing in the tube increases. In the case of FIG. 5, the positive electrode return pipe 110 is made thinner than the negative electrode return pipe 111, so that the pressure loss of the positive electrode return pipe 110 is larger than the pressure loss of the negative electrode return pipe 111. As a result, the pressure of the positive electrode electrolyte in the cell stack 2 becomes higher than the pressure of the negative electrode electrolyte, and the pressure of the positive electrode electrolyte acting on the diaphragm 101 in the cell stack 2 is larger than the pressure of the negative electrode electrolyte. The differential pressure state can be created.

図示しないが、負極用往路管１０９を、正極用往路管１０８よりも細くすることで、差圧形成機構６Ｂを形成しても構わない。この場合、セルスタック２内の負極電解液の圧力が低くなり、相対的に正極電解液の圧力が負極電解液の圧力よりも大きい状態が作り出される。もちろん、復路管１１０，１１１の太さを変える構成と、往路管１０８，１０９の太さを変える構成と、を組み合わせて差圧形成機構６Ｂを形成することもできる。   Although not shown, the differential pressure forming mechanism 6 </ b> B may be formed by making the negative electrode outward tube 109 thinner than the positive electrode outward tube 108. In this case, the pressure of the negative electrode electrolyte in the cell stack 2 is reduced, and a state in which the pressure of the positive electrode electrolyte is relatively larger than the pressure of the negative electrode electrolyte is created. Of course, the differential pressure forming mechanism 6B can be formed by combining the configuration of changing the thickness of the return pipes 110 and 111 and the configuration of changing the thickness of the outgoing pipes 108 and 109.

［正負の管路の経路を変える］
図６には、正極用復路管１１０を、負極用復路管１１１よりも複雑に屈曲させることで形成した差圧形成機構６Ｃが示されている。管の屈曲箇所が多いと、管内を流れる電解液の圧力損失が増大する。図６の場合は、正極用復路管１１０を負極用復路管１１１よりも複雑に屈曲させているので、正極用復路管１１０の圧力損失が負極用復路管１１１の圧力損失よりも大きくなる。その結果、セルスタック２内の正極電解液の圧力が負極電解液の圧力よりも高くなり、セルスタック２内の隔膜１０１に作用する正極電解液の圧力が負極電解液の圧力よりも大きい第一の差圧状態を作り出すことができる。 [Change the path of the positive and negative pipelines]
FIG. 6 shows a differential pressure forming mechanism 6 </ b> C formed by bending the positive return pipe 110 more complicatedly than the negative return pipe 111. If there are many bent portions of the tube, the pressure loss of the electrolyte flowing in the tube increases. In the case of FIG. 6, since the positive return pipe 110 is bent more complicatedly than the negative return pipe 111, the pressure loss of the positive return pipe 110 is larger than the pressure loss of the negative return pipe 111. As a result, the pressure of the positive electrode electrolyte in the cell stack 2 becomes higher than the pressure of the negative electrode electrolyte, and the pressure of the positive electrode electrolyte acting on the diaphragm 101 in the cell stack 2 is larger than the pressure of the negative electrode electrolyte. The differential pressure state can be created.

図示しないが、負極用往路管１０９を、正極用往路管１０８よりも複雑に屈曲させることで、差圧形成機構６Ｃを形成しても構わない。もちろん、復路管１１０，１１１の屈曲状態を変える構成と、往路管１０８，１０９の屈曲状態を変える構成と、を組み合わせて差圧形成機構６Ｃを形成することもできる。   Although not shown, the differential pressure forming mechanism 6C may be formed by bending the negative electrode outward tube 109 more complicatedly than the positive electrode outward tube 108. Of course, the differential pressure forming mechanism 6C can be formed by combining the configuration of changing the bent state of the return pipes 110 and 111 and the configuration of changing the bent state of the outgoing pipes 108 and 109.

［正負の管路のバルブの開度を変える］
図１に示すＲＦ電池１の正極用管路と負極用管路にはそれぞれ、図示しない複数のバルブが存在する。バルブは、セルスタック２への電解液の循環を停止する際などに利用される。これらバルブを利用して差圧形成機構を形成することもできる。例えば、正極用復路管１１０のバルブを、負極用復路管１１１のバルブよりも絞る（開度を小さくする）ことで、正極用復路管１１０の圧力損失を負極用復路管１１１の圧力損失よりも大きくできる。その結果、セルスタック２内の正極電解液の圧力が負極電解液の圧力よりも高くなり、セルスタック２内の隔膜１０１に作用する正極電解液の圧力が負極電解液の圧力よりも高い第一の差圧状態を作り出すことができる。 [Change the valve opening of the positive and negative pipes]
A plurality of valves (not shown) exist in each of the positive electrode conduit and the negative electrode conduit of the RF battery 1 shown in FIG. The valve is used when the circulation of the electrolyte solution to the cell stack 2 is stopped. These valves can be used to form a differential pressure forming mechanism. For example, the pressure loss of the positive return pipe 110 is made smaller than the pressure loss of the negative return pipe 111 by narrowing the valve of the positive return pipe 110 than the valve of the negative return pipe 111 (reducing the opening). Can be bigger. As a result, the pressure of the positive electrode electrolyte in the cell stack 2 becomes higher than the pressure of the negative electrode electrolyte, and the pressure of the positive electrode electrolyte acting on the diaphragm 101 in the cell stack 2 is higher than the pressure of the negative electrode electrolyte. The differential pressure state can be created.

負極用往路管１０９のバルブを、正極用往路管１０８のバルブよりも絞ることでも、セルスタック２内の負極電解液の圧力を低くして、上記差圧状態を作り出すことができる。もちろん、復路管１１０，１１１のバルブの開度を変える構成と、往路管１０８，１０９のバルブの開度を変える構成と、を組み合わせて差圧形成機構を形成することもできる。   The pressure difference of the negative electrode electrolyte in the cell stack 2 can also be reduced by reducing the valve of the negative electrode forward pipe 109 more than the valve of the positive electrode outgoing pipe 108. Of course, the differential pressure forming mechanism can be formed by combining the configuration of changing the opening degree of the valves of the return pipes 110 and 111 and the configuration of changing the opening degree of the valves of the outgoing pipes 108 and 109.

［正負の熱交換器の構成を変える］
図１に示すＲＦ電池１は、正極用復路管１１０の途中に設けられる正極用熱交換器４Ｐと、負極用復路管１１１の途中に設けられる負極用熱交換器４Ｎと、を備える。これら熱交換器４Ｐ，４Ｎによっても差圧形成機構６Ｄ（図７参照）を形成することができる。 [Change the configuration of positive and negative heat exchangers]
The RF battery 1 shown in FIG. 1 includes a positive electrode heat exchanger 4P provided in the middle of the positive electrode return pipe 110 and a negative electrode heat exchanger 4N provided in the middle of the negative electrode return pipe 111. The differential pressure forming mechanism 6D (see FIG. 7) can also be formed by these heat exchangers 4P and 4N.

図７の上部には負極用熱交換器４Ｎの概略構成図が、図７の下部には正極用熱交換器４Ｐの概略構成図が示されている。熱交換器の基本的な構成は、例えば特開２０１３−２０６５６６号公報に記載のように公知である。例えば、図５に示すように、冷媒４０Ｐ（４０Ｎ）を貯留する容器４１Ｐ（４１Ｎ）内に配管４２Ｐ（４２Ｎ）を這わせることで熱交換器４Ｐ（４Ｎ）を構成することができる。配管４２Ｐ（４２Ｎ）は、復路管１１０（１１１）に繋がっており、従って、その内部には正極電解液（負極電解液）が流れる。正極電解液（負極電解液）は、配管４２Ｐ（４２Ｎ）を流れる間に、冷媒４０Ｐ（４０Ｎ）によって冷却される。冷媒４０Ｐ（４０Ｎ）は、空冷用の気体冷媒や、水冷用の液体冷媒があり、図示しない冷却機構で冷却される。ここで、配管４２Ｐ（４２Ｎ）は、復路管１１０（１１１）の一部と見做すことができる。   7 is a schematic configuration diagram of the negative electrode heat exchanger 4N, and a lower configuration of FIG. 7 is a schematic configuration diagram of the positive electrode heat exchanger 4P. The basic configuration of the heat exchanger is known as described in, for example, Japanese Patent Application Laid-Open No. 2013-206566. For example, as shown in FIG. 5, the heat exchanger 4P (4N) can be configured by placing a pipe 42P (42N) in a container 41P (41N) that stores the refrigerant 40P (40N). The pipe 42P (42N) is connected to the return pipe 110 (111), and therefore, the positive electrode electrolyte (the negative electrode electrolyte) flows therein. The positive electrode electrolyte (negative electrode electrolyte) is cooled by the refrigerant 40P (40N) while flowing through the pipe 42P (42N). The refrigerant 40P (40N) includes a gas refrigerant for air cooling and a liquid refrigerant for water cooling, and is cooled by a cooling mechanism (not shown). Here, the pipe 42P (42N) can be regarded as a part of the return pipe 110 (111).

熱交換器４Ｐ，４Ｎで差圧形成機構６Ｄを形成する場合、図示するように、正極用熱交換器４Ｐの配管４２Ｐを、負極用熱交換器４Ｎの配管４２Ｎよりも長くすれば良い。そうすることで、復路管１１０，１１１の長さを変化させた差圧形成機構６Ａと同様の理由により、隔膜１０１に作用する正極電解液の圧力が負極電解液の圧力よりも高い差圧状態を作り出すことができる。   When the differential pressure forming mechanism 6D is formed by the heat exchangers 4P and 4N, the pipe 42P of the positive electrode heat exchanger 4P may be made longer than the pipe 42N of the negative electrode heat exchanger 4N as illustrated. By doing so, for the same reason as the differential pressure forming mechanism 6A in which the lengths of the return pipes 110 and 111 are changed, the pressure difference of the positive electrode electrolyte acting on the diaphragm 101 is higher than the pressure of the negative electrode electrolyte. Can produce.

その他、配管４２Ｐを配管４２Ｎよりも細くする、あるいは配管４２Ｐの屈曲箇所を配管４２Ｎの屈曲箇所よりも多くすることでも、上記差圧状態を作り出すことができる。もちろん、配管長、配管太さ、配管の屈曲状態を組み合わせて上記差圧状態を作り出しても良い。なお、正極用熱交換器４Ｐのみを設けて、負極用熱交換器４Ｎを設けないことでも、上記差圧状態を作り出すことができる。   In addition, the above-mentioned differential pressure state can also be created by making the pipe 42P thinner than the pipe 42N, or by making the bent part of the pipe 42P more than the bent part of the pipe 42N. Of course, the differential pressure state may be created by combining the pipe length, the pipe thickness, and the bent state of the pipe. The differential pressure state can also be created by providing only the positive electrode heat exchanger 4P and not the negative electrode heat exchanger 4N.

［その他の方策］
図１の正極用タンク１０６を負極用タンク１０７よりも高く配設することで、上記差圧状態を形成することもできる。また、正極用復路管１１０を負極用復路管１１１より高い位置に取回すことでも上記差圧状態を形成することができる。 [Other measures]
By arranging the positive electrode tank 106 in FIG. 1 higher than the negative electrode tank 107, the above-described differential pressure state can be formed. The differential pressure state can also be formed by routing the positive return pipe 110 to a position higher than the negative return pipe 111.

［組み合わせについて］
以上説明した各差圧形成機構は、単独あるいは組み合わせて用いることができる。例えば、管路の長さを変えることと、管路の太さを変えることと、を組み合わせると、所望の差圧状態を形成し易い。構成の組み合わせによっては、隔膜１０１の全面にわたって隔膜１０１に作用する正極電解液の圧力を負極電解液の圧力よりも大きくした第一の差圧状態を作り出すことも可能である。例えば、図５を参照する差圧形成機構６Ｂを採用する場合、正極用復路管１１０の内径を、負極用復路管１１１の内径の８０％以下とすれば、電池セル１００内の隔膜１０１に作用する正極電解液の圧力が、隔膜１０１に作用する負極電解液の圧力よりも高い第一の差圧状態を作り出すことができる。 [About combination]
Each of the differential pressure forming mechanisms described above can be used alone or in combination. For example, a combination of changing the length of the pipe line and changing the thickness of the pipe line can easily form a desired differential pressure state. Depending on the combination of configurations, it is also possible to create a first differential pressure state in which the pressure of the positive electrode electrolyte acting on the diaphragm 101 over the entire surface of the diaphragm 101 is larger than the pressure of the negative electrode electrolyte. For example, when the differential pressure forming mechanism 6B referring to FIG. 5 is employed, if the inner diameter of the positive electrode return pipe 110 is 80% or less of the inner diameter of the negative electrode return pipe 111, it acts on the diaphragm 101 in the battery cell 100. Thus, a first differential pressure state in which the pressure of the positive electrode electrolyte is higher than the pressure of the negative electrode electrolyte acting on the diaphragm 101 can be created.

［第一の差圧形成機構の効果］
以上説明した第一の差圧形成機構を利用することで、セルスタック２を分解することなく所望の差圧状態を容易に形成することができる。これに対して、特許文献１のＲＦ電池のように、セルスタック内のセルフレームにおける正極電解液の流路と負極電解液の流路とを異ならせる場合、例えば電解液の種類などの電解液の流通条件を変化させたときに、その流通条件の変化に応じて所望の差圧状態を作り出すことが難しい。流通条件に応じたセルフレームとするには、セルスタックを分解する手間、セルフレームを加工する手間、再びセルスタックを組み立てる手間がかかる上、加工したセルフレームで所望の差圧状態を達成することができない場合、さらに分解・加工・組み立てを行う必要があるからである。 [Effect of first differential pressure forming mechanism]
By using the first differential pressure forming mechanism described above, a desired differential pressure state can be easily formed without disassembling the cell stack 2. On the other hand, when the flow path of the positive electrode electrolyte and the flow path of the negative electrode electrolyte in the cell frame in the cell stack are different as in the RF battery of Patent Document 1, for example, the electrolyte such as the type of the electrolyte When the flow conditions are changed, it is difficult to create a desired differential pressure state according to the change in the flow conditions. To make the cell frame suitable for the distribution conditions, it takes time to disassemble the cell stack, time to process the cell frame, time to assemble the cell stack again, and achieve the desired differential pressure state with the processed cell frame. This is because if it is not possible, further disassembly, processing, and assembly are required.

＜実施形態２＞
実施形態２では、図１に示すＲＦ電池１において、セルスタック２内に正極電解液と負極電解液を循環させるときにも、両電解液の循環を停止するときにも、隔膜１０１に作用する負極電解液の圧力が正極電解液の圧力よりも大きい第二の差圧状態（白抜き矢印の方向に圧力が作用する状態）を維持する例を説明する。 <Embodiment 2>
In Embodiment 2, the RF battery 1 shown in FIG. 1 acts on the diaphragm 101 both when the positive and negative electrolytes are circulated in the cell stack 2 and when the circulation of both electrolytes is stopped. An example of maintaining a second differential pressure state (a state in which the pressure acts in the direction of the white arrow) where the pressure of the negative electrode electrolyte is higher than the pressure of the positive electrode electrolyte will be described.

上記第二の差圧状態は、流量制御部５によって負極用循環機構３Ｎのポンプ１１３からの負極電解液の送液量を、正極用循環機構３Ｐのポンプ１１２からの正極電解液の送液量よりも大きくすることで、作り出される。   In the second differential pressure state, the flow rate control unit 5 controls the flow rate of the negative electrode electrolyte from the pump 113 of the negative electrode circulation mechanism 3N, and the flow rate of the positive electrode electrolyte from the pump 112 of the positive electrode circulation mechanism 3P. It is produced by making it bigger.

さらに流量制御部５は、両電解液の循環を停止する際にも、上記第二の差圧状態を維持できるように、ポンプ１１２，１１３を制御する。代表的な二つの制御パターンを図８、図９に基づいて説明する。図８，９の見方は、実施形態１の図２，３と同様である。   Furthermore, the flow rate control unit 5 controls the pumps 112 and 113 so that the second differential pressure state can be maintained even when the circulation of both electrolytic solutions is stopped. Two typical control patterns will be described with reference to FIGS. The views of FIGS. 8 and 9 are the same as those of FIGS.

［制御パターンＩＩＩ］
図８のグラフに示すように、制御パターンＩＩＩでは、負極電解液の送液量を正極電解液の送液量よりも大きくして両電解液を循環させた状態から、時刻ｔ０で両電解液の循環を停止し始める。その際、負極電解液の送液量（循環量）の減少速度を、正極電解液の送液量（循環量）の減少速度よりも大きくしている。そして、時刻ｔ１で両電解液の送液をほぼ同時に停止する。 [Control Pattern III]
As shown in the graph of FIG. 8, in the control pattern III, both electrolyte solutions are supplied at a time t0 from the state in which both electrolyte solutions are circulated with the negative electrode electrolyte solution supplied larger than the positive electrode electrolyte supply amount. Start to stop circulating. At this time, the rate of decrease in the amount (circulation amount) of the negative electrode electrolyte is set to be greater than the rate of decrease in the amount (circulation amount) of the positive electrode electrolyte. At time t1, the feeding of both electrolytes is stopped almost simultaneously.

上記制御パターンＩＩＩによれば、両電解液の送液量（循環量）の差を徐々に小さくしながら両電解液の循環を停止することができる。その結果、両電解液の循環を停止するまでの間、隔膜１０１（図１参照）に作用する応力を徐々に小さくすることができるため、隔膜１０１の損傷を効果的に防止することができる。   According to the control pattern III, the circulation of both electrolytic solutions can be stopped while gradually reducing the difference in the amount (circulation amount) of both electrolytic solutions. As a result, since the stress acting on the diaphragm 101 (see FIG. 1) can be gradually reduced until the circulation of both electrolytes is stopped, damage to the diaphragm 101 can be effectively prevented.

［制御パターンＩＶ］
図９のグラフに示すように、制御パターンＩＶでも、時刻ｔ０で両電解液の循環を停止し始める。ここで、制御パターンＩＶでは、正極電解液の送液量（循環量）の減少速度と、負極電解液の送液量（循環量）の減少速度と、を同程度としている。もともと、正極電解液の送液量が負極電解液の送液量よりも小さかったために、両電解液の送液量の減少速度が同程度であると、時刻ｔ２で正極電解液の送液が停止し、その後、時刻ｔ３で負極電解液の送液が停止する。つまり、正極電解液の循環が停止した後も負極電解液がセルスタック２（図１参照）内を循環することになるため、両電解液の循環が停止する瞬間まで、確実に第二の差圧状態を維持することができる。 [Control Pattern IV]
As shown in the graph of FIG. 9, even in the control pattern IV, the circulation of both electrolytes starts to be stopped at time t0. Here, in the control pattern IV, the rate of decrease in the amount (circulation amount) of the positive electrode electrolyte is substantially the same as the rate of decrease in the amount (circulation amount) of the negative electrode electrolyte. Originally, since the amount of the positive electrode electrolyte supplied was smaller than the amount of the negative electrode electrolyte supplied, the rate of decrease in the amount of electrolyte supplied by both electrolytes was approximately the same. After that, the feeding of the negative electrode electrolyte stops at time t3. That is, since the negative electrode electrolyte circulates in the cell stack 2 (see FIG. 1) even after the circulation of the positive electrolyte is stopped, the second difference is surely ensured until the moment when the circulation of both electrolytes is stopped. The pressure state can be maintained.

なお、図１に示すＲＦ電池１の正極用管路と負極用管路にはそれぞれ、図示しない複数のバルブが存在する。それらバルブの開度・開閉回数を流量制御部５に制御させても構わない。そうすることで、上記二つの制御パターンを行い易くなる。   A plurality of valves (not shown) exist in each of the positive electrode conduit and the negative electrode conduit of the RF battery 1 shown in FIG. You may make the flow control part 5 control the opening degree and the frequency | count of opening / closing of these valves. By doing so, it becomes easy to perform the two control patterns.

≪循環停止時に係る構成≫
図１に示す上記流量制御部５の制御によって両電解液の循環を停止した後も、隔膜１０１に作用する負極電解液の圧力が正極電解液の圧力よりも大きい第二の差圧状態を維持することが好ましい。両電解液が循環していないときに差圧状態が維持されていれば、両電解液の循環を再開する際、負極電解液を循環させるポンプ１１３の始動が何らかの理由で正極電解液を循環させるポンプ１１２の始動より遅れるなどしても、隔膜１０１に作用する正極電解液の圧力が負極電解液の圧力よりも高くなる逆差圧状態となり難いからである。 ≪Configuration related to circulation stop≫
Even after the circulation of both electrolytes is stopped by the control of the flow rate control unit 5 shown in FIG. 1, the second differential pressure state in which the pressure of the negative electrode electrolyte acting on the diaphragm 101 is larger than the pressure of the positive electrode electrolyte is maintained. It is preferable to do. If the differential pressure state is maintained when both electrolytes are not circulated, when the circulation of both electrolytes is resumed, the start of the pump 113 that circulates the anode electrolyte causes the cathode electrolyte to circulate for some reason. This is because even if it is delayed from the start of the pump 112, it is difficult to achieve a reverse differential pressure state in which the pressure of the positive electrode electrolyte acting on the diaphragm 101 is higher than the pressure of the negative electrode electrolyte.

両電解液の循環が循環していないときに上記第二の差圧状態を維持するには、例えば負極用タンク１０７を正極用タンク１０６よりも高い位置に配置すると良い。そして、両電解液の循環を停止した後も、セルスタック２内に両電解液を満たしたままとしておく。そうすることで、両電解液が循環していなくても、位置エネルギーによって第二の差圧状態を維持することができる。   In order to maintain the second differential pressure state when both the electrolytes are not circulated, for example, the negative electrode tank 107 may be disposed at a higher position than the positive electrode tank 106. Then, even after the circulation of both electrolytes is stopped, the cell stack 2 is filled with both electrolytes. By doing so, even if both electrolytes are not circulating, the second differential pressure state can be maintained by the potential energy.

≪第二の差圧状態を形成し易くするための構成≫
上記ポンプ１１２，１１３からの送液量の差に加えて、第二の差圧状態を形成し易くするための第二の差圧形成機構をＲＦ電池１に設けても良い。第二の差圧形成機構は、ＲＦ電池１に備わる既存の部材の構成（主として寸法）を変えること、具体的には正極用循環機構３Ｐと負極用循環機構３Ｎとに構成上の差異を設けることで形成することができる。以下、第二の差圧形成機構の一形態を図１０〜図１３に基づいて説明する。図１０〜図１２ではタンク及びポンプを省略し、図１３ではさらにセルスタックも省略している。 ≪Configuration to facilitate the formation of the second differential pressure state≫
In addition to the difference in the amount of liquid fed from the pumps 112 and 113, the RF battery 1 may be provided with a second differential pressure forming mechanism for facilitating the formation of the second differential pressure state. The second differential pressure forming mechanism changes the configuration (mainly dimensions) of the existing members provided in the RF battery 1, and specifically provides a structural difference between the positive electrode circulation mechanism 3P and the negative electrode circulation mechanism 3N. Can be formed. Hereinafter, an embodiment of the second differential pressure forming mechanism will be described with reference to FIGS. 10 to 12, the tank and the pump are omitted, and the cell stack is also omitted in FIG.

［正負の管路の長さを変える］
図１０には、負極用復路管１１１を、正極用復路管１１０よりも長くすることで形成した差圧形成機構６Ｅが示されている。管を長くすると、管内を流れる電解液の圧力損失が増大する。図１０の場合は、負極用復路管１１１を正極用復路管１１０よりも長くしているので、負極用復路管１１１の圧力損失が正極用復路管１１０の圧力損失よりも大きくなる。その結果、セルスタック２内の負極電解液の圧力が正極電解液の圧力よりも高くなり、セルスタック２内の隔膜１０１の全面にわたって隔膜１０１に作用する負極電解液の圧力が正極電解液の圧力よりも大きい第二の差圧状態を作り出すことができる。 [Change the length of the positive and negative pipelines]
FIG. 10 shows a differential pressure forming mechanism 6E formed by making the return pipe 111 for the negative electrode longer than the return pipe 110 for the positive electrode. When the tube is lengthened, the pressure loss of the electrolyte flowing in the tube increases. In the case of FIG. 10, the negative electrode return pipe 111 is longer than the positive electrode return pipe 110, so that the pressure loss of the negative electrode return pipe 111 is larger than the pressure loss of the positive electrode return pipe 110. As a result, the pressure of the negative electrode electrolyte in the cell stack 2 becomes higher than the pressure of the positive electrode electrolyte, and the pressure of the negative electrode electrolyte acting on the diaphragm 101 over the entire surface of the diaphragm 101 in the cell stack 2 is the pressure of the positive electrode electrolyte. A second differential pressure state that is larger than that can be created.

図示しないが、正極用往路管１０８を、負極用往路管１０９よりも長くすることで、差圧形成機構６Ｅを形成しても構わない。この場合、セルスタック２内の正極電解液の圧力が低くなり、相対的に負極電解液の圧力が正極電解液の圧力よりも大きい状態が作り出される。もちろん、復路管１１０，１１１の長さを変える構成と、往路管１０８，１０９の長さを変える構成と、を組み合わせて差圧形成機構６Ａを形成することもできる。   Although not shown, the differential pressure forming mechanism 6E may be formed by making the positive electrode outward tube 108 longer than the negative electrode outward tube 109. In this case, the pressure of the positive electrode electrolyte in the cell stack 2 is lowered, and a state in which the pressure of the negative electrode electrolyte is relatively larger than the pressure of the positive electrode electrolyte is created. Of course, the differential pressure forming mechanism 6A can be formed by combining the configuration in which the lengths of the return pipes 110 and 111 are changed and the configuration in which the lengths of the outgoing pipes 108 and 109 are changed.

［正負の管路の太さを変える］
図１１には、負極用復路管１１１を、正極用復路管１１０よりも細くすることで形成した差圧形成機構６Ｆが示されている。管を細くすると、管内を流れる電解液の圧力損失が増大する。図１１の場合は、負極用復路管１１１を正極用復路管１１０よりも細くしているので、負極用復路管１１１の圧力損失が正極用復路管１１０の圧力損失よりも大きくなる。その結果、セルスタック２内の負極電解液の圧力が正極電解液の圧力よりも高くなり、セルスタック２内の隔膜１０１の全面にわたって隔膜１０１に作用する負極電解液の圧力が正極電解液の圧力よりも大きい第二の差圧状態を作り出すことができる。 [Change thickness of positive and negative pipe lines]
FIG. 11 shows a differential pressure forming mechanism 6 </ b> F formed by making the negative electrode return pipe 111 thinner than the positive electrode return pipe 110. When the tube is made thinner, the pressure loss of the electrolyte flowing in the tube increases. In the case of FIG. 11, the negative electrode return pipe 111 is made thinner than the positive electrode return pipe 110, so that the pressure loss of the negative electrode return pipe 111 is larger than the pressure loss of the positive electrode return pipe 110. As a result, the pressure of the negative electrode electrolyte in the cell stack 2 becomes higher than the pressure of the positive electrode electrolyte, and the pressure of the negative electrode electrolyte acting on the diaphragm 101 over the entire surface of the diaphragm 101 in the cell stack 2 is the pressure of the positive electrode electrolyte. A second differential pressure state that is larger than that can be created.

図示しないが、正極用往路管１０８を、負極用往路管１０９よりも細くすることで、差圧形成機構６Ｆを形成しても構わない。この場合、セルスタック２内の正極電解液の圧力が低くなり、相対的に負極電解液の圧力が正極電解液の圧力よりも大きい状態が作り出される。もちろん、復路管１１０，１１１の太さを変える構成と、往路管１０８，１０９の太さを変える構成と、を組み合わせて差圧形成機構６Ｆを形成することもできる。   Although not shown, the differential pressure forming mechanism 6 </ b> F may be formed by making the positive electrode outward tube 108 thinner than the negative electrode outward tube 109. In this case, the pressure of the positive electrode electrolyte in the cell stack 2 is lowered, and a state in which the pressure of the negative electrode electrolyte is relatively larger than the pressure of the positive electrode electrolyte is created. Of course, the differential pressure forming mechanism 6F can be formed by combining the configuration of changing the thickness of the return pipes 110 and 111 and the configuration of changing the thickness of the outgoing pipes 108 and 109.

［正負の管路の経路を変える］
図１２には、負極用復路管１１１を、正極用復路管１１０よりも複雑に屈曲させることで形成した差圧形成機構６Ｇが示されている。管の屈曲箇所が多いと、管内を流れる電解液の圧力損失が増大する。図１２の場合は、負極用復路管１１１を正極用復路管１１０よりも複雑に屈曲させているので、負極用復路管１１１の圧力損失が正極用復路管１１０の圧力損失よりも大きくなる。その結果、セルスタック２内の負極電解液の圧力が正極電解液の圧力よりも高くなり、セルスタック２内の隔膜１０１の全面にわたって隔膜１０１に作用する負極電解液の圧力が正極電解液の圧力よりも大きい第二の差圧状態を作り出すことができる。 [Change the path of the positive and negative pipelines]
FIG. 12 shows a differential pressure forming mechanism 6G formed by bending the negative electrode return pipe 111 more complicatedly than the positive electrode return pipe 110. If there are many bent portions of the tube, the pressure loss of the electrolyte flowing in the tube increases. In the case of FIG. 12, the negative electrode return pipe 111 is bent more complicatedly than the positive electrode return pipe 110, so that the pressure loss of the negative electrode return pipe 111 is larger than the pressure loss of the positive electrode return pipe 110. As a result, the pressure of the negative electrode electrolyte in the cell stack 2 becomes higher than the pressure of the positive electrode electrolyte, and the pressure of the negative electrode electrolyte acting on the diaphragm 101 over the entire surface of the diaphragm 101 in the cell stack 2 is the pressure of the positive electrode electrolyte. A second differential pressure state that is larger than that can be created.

図示しないが、正極用往路管１０８を、負極用往路管１０９よりも複雑に屈曲させることで、差圧形成機構６Ｇを形成しても構わない。もちろん、復路管１１０，１１１の屈曲状態を変える構成と、往路管１０８，１０９の屈曲状態を変える構成と、を組み合わせて差圧形成機構６Ｇを形成することもできる。   Although not shown, the differential pressure forming mechanism 6G may be formed by bending the positive electrode outward tube 108 more complicatedly than the negative electrode outward tube 109. Of course, the differential pressure forming mechanism 6G can be formed by combining the configuration of changing the bent state of the return pipes 110 and 111 and the configuration of changing the bent state of the outgoing pipes 108 and 109.

［正負の管路のバルブの開度を変える］
図１に示すＲＦ電池１の正極用管路と負極用管路にはそれぞれ、図示しない複数のバルブが存在する。バルブは、セルスタック２への電解液の循環を停止する際などに利用される。これらバルブを利用して差圧形成機構を形成することもできる。例えば、負極用復路管１１１のバルブを、正極用復路管１１０のバルブよりも絞る（開度を小さくする）ことで、負極用復路管１１１の圧力損失を正極用復路管１１０の圧力損失よりも大きくできる。その結果、セルスタック２内の負極電解液の圧力が正極電解液の圧力よりも高くなり、セルスタック２内の隔膜１０１の全面にわたって隔膜１０１に作用する負極電解液の圧力が正極電解液の圧力よりも高い第二の差圧状態を作り出すことができる。 [Change the valve opening of the positive and negative pipes]
A plurality of valves (not shown) exist in each of the positive electrode conduit and the negative electrode conduit of the RF battery 1 shown in FIG. The valve is used when the circulation of the electrolyte solution to the cell stack 2 is stopped. These valves can be used to form a differential pressure forming mechanism. For example, the pressure loss of the negative return pipe 111 is made smaller than the pressure loss of the positive return pipe 110 by narrowing the valve of the negative return pipe 111 than the valve of the positive return pipe 110 (reducing the opening). Can be big. As a result, the pressure of the negative electrode electrolyte in the cell stack 2 becomes higher than the pressure of the positive electrode electrolyte, and the pressure of the negative electrode electrolyte acting on the diaphragm 101 over the entire surface of the diaphragm 101 in the cell stack 2 is the pressure of the positive electrode electrolyte. Higher second differential pressure state can be created.

正極用往路管１０８のバルブを、負極用往路管１０９のバルブよりも絞ることでも、セルスタック２内の正極電解液の圧力を低くして、上記差圧状態を作り出すことができる。もちろん、復路管１１０，１１１のバルブの開度を変える構成と、往路管１０８，１０９のバルブの開度を変える構成と、を組み合わせて差圧形成機構を形成することもできる。   The pressure difference of the positive electrode electrolyte in the cell stack 2 can also be reduced by creating a valve for the positive electrode outward pipe 108 that is narrower than the valve for the negative electrode outgoing pipe 109. Of course, the differential pressure forming mechanism can be formed by combining the configuration of changing the opening degree of the valves of the return pipes 110 and 111 and the configuration of changing the opening degree of the valves of the outgoing pipes 108 and 109.

［正負の熱交換器の構成を変える］
図１に示すＲＦ電池１は、正極用復路管１１０の途中に設けられる正極用熱交換器４Ｐと、負極用復路管１１１の途中に設けられる負極用熱交換器４Ｎと、を備える。これら熱交換器４Ｐ，４Ｎによっても差圧形成機構６Ｈ（図１３参照）を形成することができる。 [Change the configuration of positive and negative heat exchangers]
The RF battery 1 shown in FIG. 1 includes a positive electrode heat exchanger 4P provided in the middle of the positive electrode return pipe 110 and a negative electrode heat exchanger 4N provided in the middle of the negative electrode return pipe 111. The differential pressure forming mechanism 6H (see FIG. 13) can also be formed by these heat exchangers 4P and 4N.

図１３の上部には負極用熱交換器４Ｎの概略構成図が、図１３の下部には正極用熱交換器４Ｐの概略構成図が示されている。熱交換器の基本的な構成は、例えば特開２０１３−２０６５６６号公報に記載のように公知である。例えば、図１３に示すように、冷媒４０Ｐ（４０Ｎ）を貯留する容器４１Ｐ（４１Ｎ）内に配管４２Ｐ（４２Ｎ）を這わせることで熱交換器４Ｐ（４Ｎ）を構成することができる。配管４２Ｐ（４２Ｎ）は、復路管１１０（１１１）に繋がっており、従って、その内部には正極電解液（負極電解液）が流れる。正極電解液（負極電解液）は、配管４２Ｐ（４２Ｎ）を流れる間に、冷媒４０Ｐ（４０Ｎ）によって冷却される。冷媒４０Ｐ（４０Ｎ）は、空冷用の気体冷媒や、水冷用の液体冷媒があり、図示しない冷却機構で冷却される。ここで、配管４２Ｐ（４２Ｎ）は、復路管１１０（１１１）の一部と見做すことができる。   13 is a schematic configuration diagram of the negative electrode heat exchanger 4N, and a lower configuration of FIG. 13 is a schematic configuration diagram of the positive electrode heat exchanger 4P. The basic configuration of the heat exchanger is known as described in, for example, Japanese Patent Application Laid-Open No. 2013-206566. For example, as shown in FIG. 13, the heat exchanger 4P (4N) can be configured by placing a pipe 42P (42N) in a container 41P (41N) that stores the refrigerant 40P (40N). The pipe 42P (42N) is connected to the return pipe 110 (111), and therefore, the positive electrode electrolyte (the negative electrode electrolyte) flows therein. The positive electrode electrolyte (negative electrode electrolyte) is cooled by the refrigerant 40P (40N) while flowing through the pipe 42P (42N). The refrigerant 40P (40N) includes a gas refrigerant for air cooling and a liquid refrigerant for water cooling, and is cooled by a cooling mechanism (not shown). Here, the pipe 42P (42N) can be regarded as a part of the return pipe 110 (111).

熱交換器４Ｐ，４Ｎで差圧形成機構６Ｈを形成する場合、図示するように、負極用熱交換器４Ｎの配管４２Ｎを、正極用熱交換器４Ｐの配管４２Ｐよりも長くすれば良い。そうすることで、復路管１１０，１１１の長さを変化させた差圧形成機構６Ａと同様の理由により、隔膜１０１に作用する負極電解液の圧力が正極電解液の圧力よりも高い差圧状態を作り出すことができる。   When the differential pressure forming mechanism 6H is formed by the heat exchangers 4P and 4N, the pipe 42N of the negative electrode heat exchanger 4N may be made longer than the pipe 42P of the positive electrode heat exchanger 4P as illustrated. By doing so, for the same reason as the differential pressure forming mechanism 6A in which the lengths of the return pipes 110 and 111 are changed, the pressure difference of the negative electrode electrolyte acting on the diaphragm 101 is higher than the pressure of the positive electrode electrolyte. Can produce.

その他、配管４２Ｎを配管４２Ｐよりも細くする、あるいは配管４２Ｎの屈曲箇所を配管４２Ｐの屈曲箇所よりも多くすることでも、上記差圧状態を作り出すことができる。もちろん、配管長、配管太さ、配管の屈曲状態を組み合わせて上記差圧状態を作り出しても良い。なお、負極用熱交換器４Ｎのみを設けて、正極用熱交換器４Ｐを設けないことでも、上記差圧状態を作り出すことができる。   In addition, the above-mentioned differential pressure state can also be created by making the pipe 42N thinner than the pipe 42P or by making the bent part of the pipe 42N more than the bent part of the pipe 42P. Of course, the differential pressure state may be created by combining the pipe length, the pipe thickness, and the bent state of the pipe. The above differential pressure state can also be created by providing only the negative electrode heat exchanger 4N and not the positive electrode heat exchanger 4P.

［その他の方策］
図１の負極用タンク１０７を正極用タンク１０６よりも高く配設することで、上記差圧状態を形成することもできる。また、負極用復路管１１１を正極用復路管１１０より高い位置に取回すことでも上記差圧状態を形成することができる。 [Other measures]
The above-described differential pressure state can be formed by disposing the negative electrode tank 107 of FIG. 1 higher than the positive electrode tank 106. Further, the differential pressure state can also be formed by routing the negative electrode return pipe 111 to a position higher than the positive electrode return pipe 110.

［組み合わせについて］
以上説明した各差圧形成機構は、単独あるいは組み合わせて用いることができる。例えば、管路の長さを変えることと、管路の太さを変えることと、を組み合わせると、所望の差圧状態を形成し易い。構成の組み合わせによっては、隔膜１０１の全面にわたって隔膜１０１に作用する負極電解液の圧力を正極電解液の圧力よりも大きくした第二の差圧状態を作り出すことも可能である。例えば、図１１を参照する差圧形成機構６Ｆを採用する場合、負極用復路管１１１の内径を、正極用復路管１１０の内径の８０％以下とすれば、電池セル１００内の隔膜１０１に作用する負極電解液の圧力が、隔膜１０１に作用する正極電解液の圧力よりも高い第二の差圧状態を作り出すことができる。 [About combination]
Each of the differential pressure forming mechanisms described above can be used alone or in combination. For example, a combination of changing the length of the pipe line and changing the thickness of the pipe line can easily form a desired differential pressure state. Depending on the combination of configurations, it is also possible to create a second differential pressure state in which the pressure of the negative electrode electrolyte acting on the diaphragm 101 over the entire surface of the diaphragm 101 is greater than the pressure of the positive electrode electrolyte. For example, when the differential pressure forming mechanism 6F with reference to FIG. 11 is adopted, if the inner diameter of the negative electrode return pipe 111 is 80% or less of the inner diameter of the positive electrode return pipe 110, it acts on the diaphragm 101 in the battery cell 100. A second differential pressure state can be created in which the pressure of the negative electrode electrolyte is higher than the pressure of the positive electrode electrolyte acting on the diaphragm 101.

［第二の差圧形成機構の効果］
以上説明した第二の差圧形成機構を利用することで、セルスタック２を分解することなく所望の差圧状態を容易に形成することができる。これに対して、特許文献１のＲＦ電池のように、セルスタック内のセルフレームにおける正極電解液の流路と負極電解液の流路とを異ならせる場合、例えば電解液の種類などの電解液の流通条件を変化させたときに、その流通条件の変化に応じて所望の差圧状態を作り出すことが難しい。流通条件に応じたセルフレームとするには、セルスタックを分解する手間、セルフレームを加工する手間、再びセルスタックを組み立てる手間がかかる上、加工したセルフレームで所望の差圧状態を達成することができない場合、さらに分解・加工・組み立てを行う必要があるからである。 [Effect of second differential pressure forming mechanism]
By using the second differential pressure forming mechanism described above, a desired differential pressure state can be easily formed without disassembling the cell stack 2. On the other hand, when the flow path of the positive electrode electrolyte and the flow path of the negative electrode electrolyte in the cell frame in the cell stack are different as in the RF battery of Patent Document 1, for example, the electrolyte such as the type of the electrolyte When the flow conditions are changed, it is difficult to create a desired differential pressure state according to the change in the flow conditions. To make the cell frame suitable for the distribution conditions, it takes time to disassemble the cell stack, time to process the cell frame, time to assemble the cell stack again, and achieve the desired differential pressure state with the processed cell frame. This is because if it is not possible, further disassembly, processing, and assembly are required.

本発明のレドックスフロー電池およびレドックスフロー電池の運転方法は、太陽光発電、風力発電などの新エネルギーの発電に対して、発電出力の変動の安定化、発電電力の余剰時の蓄電、負荷平準化などに利用できる他、一般的な発電所に併設されて、瞬時電圧低下対策・停電対策や負荷平準化にも利用することができる。   The redox flow battery and the operation method of the redox flow battery according to the present invention include stabilization of fluctuations in power generation output, power storage when surplus generated power, load leveling for new energy generation such as solar power generation and wind power generation In addition to being used for general power plants, it can also be used for instantaneous voltage drop countermeasures, power outage countermeasures, and load leveling.

１，α レドックスフロー電池（ＲＦ電池）
２ セルスタック
１００ 電池セル
１０１ 隔膜
１０２ 正極部 １０３ 負極部 １０４ 正極電極 １０５ 負極電極
３Ｐ，１００Ｐ 正極用循環機構
１０６ 正極用タンク １０８ 正極用往路管 １１０ 正極用復路管
１１２ ポンプ（正極用送液装置）
３Ｎ，１００Ｎ 負極用循環機構
４Ｐ 正極用熱交換器
４０Ｐ 冷媒 ４１Ｐ 容器 ４２Ｐ 配管
４Ｎ 負極用熱交換器
４０Ｎ 冷媒 ４１Ｎ 容器 ４２Ｎ 配管
５ 流量制御部
６Ａ，６Ｂ，６Ｃ，６Ｄ，６Ｅ，６Ｆ，６Ｇ，６Ｈ 差圧形成機構
１０７ 負極用タンク １０９ 負極用往路管 １１１ 負極用復路管
１１３ ポンプ（負極用送液装置）
１２０ セルフレーム １２１ 双極板 １２２ 枠体
１２３，１２４ 給液用マニホールド １２５，１２６ 排液用マニホールド
１２７ シール部材
１９０ 給排板 ２１０，２２０ エンドプレート
２００ セルスタック ２００ｓ サブスタック
２３０ 締付機構 1, α Redox flow battery (RF battery)
2 Cell stack 100 Battery cell 101 Diaphragm 102 Positive electrode portion 103 Negative electrode portion 104 Positive electrode 105 Negative electrode 3P, 100P Positive electrode circulation mechanism 106 Positive electrode tank 108 Positive electrode outward tube 110 Positive electrode return tube 112 Pump (liquid supply device for positive electrode)
3N, 100N Negative electrode circulation mechanism 4P Positive electrode heat exchanger 40P Refrigerant 41P container 42P piping 4N Negative electrode heat exchanger 40N Refrigerant 41N container 42N piping 5 Flow rate control unit 6A, 6B, 6C, 6D, 6E, 6F, 6G, 6H Differential pressure forming mechanism 107 Tank for negative electrode 109 Outward pipe for negative electrode 111 Return pipe for negative electrode 113 Pump (liquid feeding device for negative electrode)
DESCRIPTION OF SYMBOLS 120 Cell frame 121 Bipolar plate 122 Frame 123,124 Manifold for liquid supply 125,126 Manifold for drainage 127 Seal member 190 Supply / discharge plate 210,220 End plate 200 Cell stack 200s Sub stack 230 Tightening mechanism

Claims (5)

正極電極、負極電極、および隔膜を有する電池セルを複数積層したセルスタックに、正極用循環機構を用いて正極電解液を循環させると共に、負極用循環機構を用いて負極電解液を循環させるレドックスフロー電池の運転方法であって、
前記正極電解液と前記負極電解液を前記セルスタックに循環させる際、一方の電解液の循環量を他方の電解液の循環量よりも多くして、前記隔膜に作用する前記一方の電解液の圧力を、前記隔膜に作用する前記他方の電解液の圧力よりも大きくした差圧状態とし、
前記正極電解液と前記負極電解液の循環量を減少させ、両電解液の循環を停止する際にも、前記一方の電解液の循環量を前記他方の電解液の循環量よりも多くして、前記差圧状態を維持するレドックスフロー電池の運転方法。 Redox flow in which a positive electrode electrolyte is circulated using a positive electrode circulation mechanism and a negative electrode electrolyte is circulated in a cell stack in which a plurality of battery cells having positive electrodes, negative electrodes, and diaphragms are stacked. A battery operating method,
When circulating the positive electrode electrolyte and the negative electrode electrolyte to the cell stack, the circulation amount of one electrolyte solution is made larger than the circulation amount of the other electrolyte solution, and the one electrolyte solution acting on the diaphragm The pressure is set to a differential pressure state larger than the pressure of the other electrolyte acting on the diaphragm,
When the circulation amount of the positive electrode electrolyte and the negative electrode electrolyte is decreased and the circulation of both electrolytes is stopped, the circulation amount of the one electrolyte solution is made larger than the circulation amount of the other electrolyte solution. The operation method of the redox flow battery which maintains the said differential pressure state. 前記正極電解液と前記負極電解液の循環を停止する際、前記一方の電解液の循環量の減少速度を、前記他方の電解液の循環量の減少速度よりも大きくし、両電解液の循環を同時に停止する請求項１に記載のレドックスフロー電池の運転方法。   When stopping the circulation of the positive electrode electrolyte and the negative electrode electrolyte, the decrease rate of the circulation amount of the one electrolyte solution is made larger than the decrease rate of the circulation amount of the other electrolyte solution, The operation method of the redox flow battery according to claim 1, wherein the two are stopped simultaneously. 前記正極電解液と前記負極電解液の循環を停止する際、前記一方の電解液の循環量の減少速度と、前記他方の電解液の循環量の減少速度と、を調整し、
前記一方の電解液の循環を、前記他方の電解液の循環よりも後に停止する請求項１に記載のレドックスフロー電池の運転方法。 When stopping the circulation of the positive electrode electrolyte and the negative electrode electrolyte, the reduction rate of the circulation amount of the one electrolyte solution and the reduction rate of the circulation amount of the other electrolyte solution are adjusted,
The method for operating a redox flow battery according to claim 1, wherein the circulation of the one electrolytic solution is stopped after the circulation of the other electrolytic solution. 前記一方の電解液を循環させる循環機構に備わる電解液のタンクを、前記他方の電解液を循環させる循環機構に備わる電解液のタンクよりも高い位置に配置し、
両電解液が循環していないときに、前記セルスタック内に両電解液を満たしたままとする請求項１〜請求項３のいずれか１項に記載のレドックスフロー電池の運転方法。 An electrolyte solution tank provided in a circulation mechanism for circulating the one electrolyte solution is disposed at a higher position than an electrolyte solution tank provided in the circulation mechanism for circulating the other electrolyte solution,
The operating method of the redox flow battery according to any one of claims 1 to 3, wherein both the electrolytes are filled in the cell stack when both the electrolytes are not circulating. 正極電極、負極電極、および隔膜を有する電池セルを複数積層したセルスタックと、前記セルスタックに正極電解液を循環させる正極用循環機構と、前記セルスタックに負極電解液を循環させる負極用循環機構と、を備えるレドックスフロー電池であって、
前記正極電解液と前記負極電解液の循環から停止までの間、一方の電解液の循環量を他方の電解液の循環量よりも多くなるように、前記正極循環機構と前記負極循環機構とを制御する流量制御部を備えるレドックスフロー電池。 A cell stack in which a plurality of battery cells having a positive electrode, a negative electrode, and a diaphragm are stacked, a positive electrode circulation mechanism that circulates a positive electrode electrolyte in the cell stack, and a negative electrode circulation mechanism that circulates a negative electrode electrolyte in the cell stack A redox flow battery comprising:
The positive electrode circulation mechanism and the negative electrode circulation mechanism are arranged so that the circulation amount of one electrolyte solution is larger than the circulation amount of the other electrolyte solution between the circulation of the positive electrode electrolyte and the negative electrode electrolyte. A redox flow battery including a flow control unit for controlling.
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