JP7091934B2 - Vehicle flow battery - Google Patents

Vehicle flow battery Download PDF

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JP7091934B2
JP7091934B2 JP2018155631A JP2018155631A JP7091934B2 JP 7091934 B2 JP7091934 B2 JP 7091934B2 JP 2018155631 A JP2018155631 A JP 2018155631A JP 2018155631 A JP2018155631 A JP 2018155631A JP 7091934 B2 JP7091934 B2 JP 7091934B2
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positive electrode
negative electrode
electrode side
electrolytic solution
member accommodating
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JP2020030964A (en
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奏 田丸
肇 恒川
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Mitsubishi Motors Corp
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    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/7072—Electromobility specific charging systems or methods for batteries, ultracapacitors, supercapacitors or double-layer capacitors
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02T90/10—Technologies relating to charging of electric vehicles
    • Y02T90/14—Plug-in electric vehicles

Description

本発明は、車両に設けるフロー電池に関する。 The present invention relates to a flow battery provided in a vehicle.

従来から、フロー型の電池が知られている（例えば、特許文献１を参照）。このような電池では、正極側電解液室に循環される正極活物質を含む正極側電解液に対して、粉末状の酸化剤を供給することによって、正極活物質を酸化させる。また、負極側電解液室に循環される負極活物質を含む負極側電解液に対して、粉末状の還元剤を供給することによって、負極活物質を還元させる。したがって、特許文献１の構成によれば、車両の走行距離を伸ばすことができる。 Conventionally, a flow type battery has been known (see, for example, Patent Document 1). In such a battery, the positive electrode active material is oxidized by supplying a powdery oxidizing agent to the positive electrode side electrolytic solution containing the positive electrode active material circulated in the positive electrode side electrolytic solution chamber. Further, the negative electrode active material is reduced by supplying a powdery reducing agent to the negative electrode side electrolytic solution containing the negative electrode active material circulated in the negative electrode side electrolytic solution chamber. Therefore, according to the configuration of Patent Document 1, the mileage of the vehicle can be extended.

特開２０１７－１１７５２７号公報JP-A-2017-117527

特許文献１の構成では、正極活物質を酸化させることによってエネルギーを消耗した酸化剤は正極電解液中に溶解しており、分離して排出するのは困難である。また、負極活物質を還元させることによってエネルギーを消耗した還元剤は負極電解液中に溶解しており、分離して排出するのは困難である。よって、酸化剤及び還元剤の供給を繰り返すことで電解液濃度は高まり、飽和濃度に達した状態では更なる供給が不可能になり、車両の走行距離を伸ばすことができない。酸化剤及び還元剤の供給を繰り返した際は、電解液の交換が必要になる。 In the configuration of Patent Document 1, the oxidant whose energy is consumed by oxidizing the positive electrode active material is dissolved in the positive electrode electrolytic solution, and it is difficult to separate and discharge the oxidant. Further, the reducing agent that has consumed energy by reducing the negative electrode active material is dissolved in the negative electrode electrolytic solution, and it is difficult to separate and discharge the reducing agent. Therefore, by repeating the supply of the oxidizing agent and the reducing agent, the concentration of the electrolytic solution increases, and when the saturation concentration is reached, further supply becomes impossible, and the mileage of the vehicle cannot be extended. When the supply of the oxidizing agent and the reducing agent is repeated, it is necessary to replace the electrolytic solution.

本発明の目的は、電解液の交換が不要で、車両の走行距離を効率良く伸ばすことができる車両用フロー電池及びその制御方法を提供することにある。 An object of the present invention is to provide a flow battery for a vehicle and a control method thereof, which do not require replacement of an electrolytic solution and can efficiently extend the mileage of the vehicle.

かかる目的を達成するために、本発明の車両用フロー電池は、正極電極が収容された正極セルと、負極電極が収容された負極セルと、を有する発電セルと、正極活物質を含む正極電解液を貯蔵する正極側溶液タンクを有し、正極側循環配管を介して正極セルと該正極側溶液タンクとの間で該正極電解液を循環させる正極側循環部と、負極活物質を含む負極電解液を貯蔵する負極側溶液タンクを有し、負極側循環配管を介して負極セルと該正極側溶液タンクとの間で該負極電解液を循環させる負極側循環部と、を備えた車両用フロー電池である。ここで、本発明の車両用フロー電池は、酸化部材を収容する酸化部材収容部を有し、正極電解液を該酸化部材収容部へ流通させる酸化部と、還元部材を収容する還元部材収容部を有し、負極電解液を該還元部材収容部へ流通させる還元部と、正極電解液の酸化部材収容部への流通状態を調整する第１流通状態調整部と、負極電解液の還元部材収容部への流通状態を調整する第２流通状態調整部と、第１流通状態調整部及び第２流通状態調整部を制御する制御部と、を有する。 In order to achieve such an object, the vehicle flow battery of the present invention has a power generation cell having a positive electrode cell containing a positive electrode and a negative electrode cell containing a negative electrode, and positive electrode electrolysis containing a positive electrode active material. It has a positive electrode side solution tank for storing the liquid, a positive electrode side circulating portion for circulating the positive electrode electrolytic solution between the positive electrode cell and the positive electrode side solution tank via a positive electrode side circulation pipe, and a negative electrode containing a negative electrode active material. For vehicles having a negative electrode side solution tank for storing the electrolytic solution and a negative electrode side circulating portion for circulating the negative electrode side electrolytic solution between the negative electrode cell and the positive electrode side solution tank via a negative electrode side circulation pipe. It is a flow battery. Here, the vehicle flow battery of the present invention has an oxidizing member accommodating portion for accommodating an oxidizing member, an oxidizing portion for distributing a positive electrode electrolytic solution to the oxidizing member accommodating portion, and a reducing member accommodating portion for accommodating the reducing member. A reducing unit that distributes the negative electrode electrolytic solution to the reducing member accommodating portion, a first distribution state adjusting unit that adjusts the distribution state of the positive electrode electrolytic solution to the oxidizing member accommodating portion, and a reducing member accommodating the negative electrode electrolytic solution. It has a second distribution state adjusting unit that adjusts the distribution state to the unit, and a control unit that controls the first distribution state adjusting unit and the second distribution state adjusting unit.

本発明によれば、電解液交換が不要で、車両の走行距離を効率良く伸ばすことができる車両用フロー電池及びその制御方法を実現することができる。 According to the present invention, it is possible to realize a flow battery for a vehicle and a control method thereof, which do not require replacement of an electrolytic solution and can efficiently extend the mileage of the vehicle.

車両に設けた第１実施形態の車両用フロー電池を示す模式図。The schematic diagram which shows the flow battery for a vehicle of 1st Embodiment provided in a vehicle. 第１実施形態の車両用フロー電池を示す模式図。The schematic diagram which shows the flow battery for a vehicle of 1st Embodiment. 第２実施形態の車両用フロー電池を示す模式図。The schematic diagram which shows the flow battery for a vehicle of 2nd Embodiment. 第３実施形態の車両用フロー電池を示す模式図。The schematic diagram which shows the flow battery for a vehicle of 3rd Embodiment.

「第１実施形態」
「車両用フロー電池１００の構成」
図１及び図２を参照して、車両１０に設けられた車両用フロー電池１００の構成（発電セル１１０、正極側循環部１２０、負極側循環部１３０、酸化部１４０、還元部１５０及び制御部１６０）と、車両１０に設けられ車両用フロー電池１００と接続された電気ユニット２０の構成を説明する。 "First embodiment"
"Structure of Flow Battery 100 for Vehicles"
With reference to FIGS. 1 and 2, the configuration of the vehicle flow battery 100 provided in the vehicle 10 (power generation cell 110, positive electrode side circulation unit 120, negative electrode side circulation unit 130, oxidation unit 140, reduction unit 150 and control unit). 160) and the configuration of the electric unit 20 provided in the vehicle 10 and connected to the vehicle flow battery 100 will be described.

「発電セル１１０の構成」
発電セル１１０は、車両１０に設けられた駆動機器２５に対して電力を供給する。発電セル１１０は、図１又は図２に示すように、正極電極１１１と、正極セル１１２と、負極電極１１３と、負極セル１１４と、隔膜１１５と、を有している。 "Configuration of power generation cell 110"
The power generation cell 110 supplies electric power to the drive device 25 provided in the vehicle 10. As shown in FIG. 1 or 2, the power generation cell 110 has a positive electrode 111, a positive electrode 112, a negative electrode 113, a negative electrode cell 114, and a diaphragm 115.

正極電極１１１は、例えば、炭素繊維からなり、板状に形成されている。正極セル１１２には、正極電極１１１が収容され、正極活物質１２１を含む正極電解液１２２が循環される。負極電極１１３は、例えば、炭素繊維からなり、板状に形成されている。負極セル１１４には、負極電極１１３が収容され、負極活物質１３１を含む負極電解液１３２が循環される。隔膜１１５は、いわゆるセパレータであり、正極セル１１２と負極セル１１４との間を区切る。隔膜１１５は、正極活物質１２１を含む正極電解液１２２と、負極活物質１３１を含む負極電解液１３２とが混ざることを防ぐ。隔膜１１５は、正極電解液１２２と負極電解液１３２との間で、イオンを通す。隔膜１１５は、例えばイオン交換膜からなる。発電セル１１０は、例えば、車両１０の前方に設けられている。 The positive electrode 111 is made of carbon fiber, for example, and is formed in a plate shape. The positive electrode cell 112 houses the positive electrode 111, and the positive electrode electrolyte 122 containing the positive electrode active material 121 is circulated. The negative electrode 113 is made of carbon fiber, for example, and is formed in a plate shape. The negative electrode cell 114 accommodates the negative electrode 113, and the negative electrode electrolytic solution 132 containing the negative electrode active material 131 is circulated. The diaphragm 115 is a so-called separator and separates the positive electrode cell 112 and the negative electrode cell 114. The diaphragm 115 prevents the positive electrode electrolyte 122 containing the positive electrode active material 121 from mixing with the negative electrode electrolytic solution 132 containing the negative electrode active material 131. The diaphragm 115 passes ions between the positive electrode electrolyte 122 and the negative electrode electrolyte 132. The diaphragm 115 is made of, for example, an ion exchange membrane. The power generation cell 110 is provided, for example, in front of the vehicle 10.

「正極側循環部１２０の構成」
正極側循環部１２０は、正極活物質１２１を含む正極電解液１２２を貯蔵する正極側溶液タンク１２３を有し、正極側循環配管（正極側循環部導入管１２４及び正極側循環部導出管１２５）を介して正極セル１１２と正極側溶液タンク１２３との間で正極電解液１２２を循環させる。換言すると、正極側循環部１２０は、発電セル１１０の正極セル１１２に対して、酸化された状態の正極活物質１２１を含む正極電解液１２２を循環させる。正極側循環部１２０は、図２に示すように、正極活物質１２１と、正極電解液１２２と、正極側溶液タンク１２３と、正極側循環部導入管１２４と、正極側循環部導出管１２５と、正極側循環用ポンプ１２６と、を有している。 "Structure of the positive electrode side circulation portion 120"
The positive electrode side circulation portion 120 has a positive electrode side solution tank 123 for storing a positive electrode electrolytic solution 122 containing a positive electrode active material 121, and a positive electrode side circulation pipe (positive electrode side circulation portion introduction pipe 124 and positive electrode side circulation portion lead-out pipe 125). The positive electrode electrolyte 122 is circulated between the positive electrode cell 112 and the positive electrode side solution tank 123. In other words, the positive electrode side circulation unit 120 circulates the positive electrode electrolyte 122 containing the oxidized positive electrode active material 121 with the positive electrode cell 112 of the power generation cell 110. As shown in FIG. 2, the positive electrode side circulation portion 120 includes a positive electrode active material 121, a positive electrode electrolytic solution 122, a positive electrode side solution tank 123, a positive electrode side circulation portion introduction pipe 124, and a positive electrode side circulation portion lead-out pipe 125. , And a positive electrode side circulation pump 126.

正極活物質１２１は、例えば鉄イオンからなる。図２に示すように、充電時において、２価の正極活物質１２１ａは、正極電極１１１から電子が流出することによって、３価の正極活物質１２１ｂに酸化される。なお、正極活物質１２１には、様々な材料を適用することができ、負極活物質よりも貴な電位を取る正極活物質を適用することができる。正極電解液１２２は、例えば、溶媒がプロピレンカーボネートで、電解質がヘキサフルオロリン酸リチウム（ＬｉＰＦ６）からなる。正極側溶液タンク１２３は、正極活物質１２１を含む正極電解液１２２を収容する容器である。 The positive electrode active material 121 is made of, for example, iron ions. As shown in FIG. 2, during charging, the divalent positive electrode active material 121a is oxidized to the trivalent positive electrode active material 121b by the outflow of electrons from the positive electrode electrode 111. Various materials can be applied to the positive electrode active material 121, and a positive electrode active material having a potential higher than that of the negative electrode active material can be applied. The positive electrode electrolyte 122 has, for example, a solvent of propylene carbonate and an electrolyte of lithium hexafluorophosphate (LiPF 6 ). The positive electrode side solution tank 123 is a container for accommodating the positive electrode electrolytic solution 122 containing the positive electrode active material 121.

正極側循環部導入管１２４は、正極側溶液タンク１２３と正極セル１１２との間に接続された配管である。正極側循環部導入管１２４を用いて、正極側溶液タンク１２３から正極セル１１２に対して、酸化された状態の正極活物質１２１を含む正極電解液１２２が導入（供給）される。正極側循環部導出管１２５は、正極セル１１２と正極側溶液タンク１２３との間に接続された配管である。正極側循環部導出管１２５を用いて、正極セル１１２から正極側溶液タンク１２３に対して、還元された状態の正極活物質１２１を含む正極電解液１２２が導出（排出）される。正極側循環用ポンプ１２６は、例えば正極側循環部導出管１２５に接続された送液用のポンプである。正極側循環用ポンプ１２６を用いて、正極側溶液タンク１２３と正極セル１１２との間において、正極活物質１２１を含む正極電解液１２２を循環させる。 The positive electrode side circulation portion introduction pipe 124 is a pipe connected between the positive electrode side solution tank 123 and the positive electrode cell 112. The positive electrode electrolytic solution 122 containing the oxidized positive electrode active material 121 is introduced (supplied) from the positive electrode side solution tank 123 to the positive electrode cell 112 by using the positive electrode side circulation portion introduction tube 124. The positive electrode side circulation portion lead-out pipe 125 is a pipe connected between the positive electrode cell 112 and the positive electrode side solution tank 123. The positive electrode electrolytic solution 122 containing the reduced positive electrode active material 121 is led out (discharged) from the positive electrode cell 112 to the positive electrode side solution tank 123 by using the positive electrode side circulation portion lead-out tube 125. The positive electrode side circulation pump 126 is, for example, a liquid feeding pump connected to the positive electrode side circulation portion lead-out pipe 125. The positive electrode side circulation pump 126 is used to circulate the positive electrode electrolytic solution 122 containing the positive electrode active material 121 between the positive electrode side solution tank 123 and the positive electrode cell 112.

「負極側循環部１３０の構成」
負極側循環部１３０は、負極活物質１３１を含む負極電解液１３２を貯蔵する負極側溶液タンク１３３を有し、負極側循環配管（負極側循環部導入管１３４及び負極側循環部導出管１３５）を介して負極セル１１４と正極側溶液タンク１２３との間で負極電解液１３２を循環させる。換言すると、負極側循環部１３０は、発電セル１１０の負極セル１１４に対して、還元された状態の負極活物質１３１を含む負極電解液１３２を循環させる。負極側循環部１３０は、図２に示すように、負極活物質１３１と、負極電解液１３２と、負極側溶液タンク１３３と、負極側循環部導入管１３４と、負極側循環部導出管１３５と、負極側循環用ポンプ１３６と、を有している。 "Structure of the negative electrode side circulation portion 130"
The negative electrode side circulation portion 130 has a negative electrode side solution tank 133 for storing the negative electrode side solution 132 containing the negative electrode active material 131, and the negative electrode side circulation pipe (negative electrode side circulation portion introduction pipe 134 and negative electrode side circulation portion lead-out pipe 135). The negative electrode electrolyte 132 is circulated between the negative electrode cell 114 and the positive electrode side solution tank 123. In other words, the negative electrode side circulation unit 130 circulates the negative electrode electrolytic solution 132 containing the negative electrode active material 131 in the reduced state with the negative electrode cell 114 of the power generation cell 110. As shown in FIG. 2, the negative electrode side circulation portion 130 includes a negative electrode active material 131, a negative electrode electrolytic solution 132, a negative electrode side solution tank 133, a negative electrode side circulation portion introduction pipe 134, and a negative electrode side circulation portion lead-out pipe 135. , And a negative electrode side circulation pump 136.

負極活物質１３１は、例えばコバルトイオンからなる。図２に示すように、充電時において、３価の負極活物質１３１ａは、負極電極１１３から電子が流入することによって、２価の負極活物質１３１ｂに還元される。なお、負極活物質１３１には、様々な材料を適用することができ、正極活物質よりも卑な電位を持つ負極活物質の材料も適用することができる。負極電解液１３２は、例えば、溶媒がプロピレンカーボネートで、電解質がヘキサフルオロリン酸リチウム（ＬｉＰＦ６）からなる。負極側溶液タンク１３３は、負極活物質１３１を含む負極電解液１３２を収容する容器である。 The negative electrode active material 131 is made of, for example, cobalt ions. As shown in FIG. 2, during charging, the trivalent negative electrode active material 131a is reduced to the divalent negative electrode active material 131b by the inflow of electrons from the negative electrode electrode 113. Various materials can be applied to the negative electrode active material 131, and a material of a negative electrode active material having a lower potential than that of the positive electrode active material can also be applied. In the negative electrode electrolyte 132, for example, the solvent is propylene carbonate and the electrolyte is lithium hexafluorophosphate (LiPF 6 ). The negative electrode side solution tank 133 is a container for accommodating the negative electrode electrolytic solution 132 containing the negative electrode active material 131.

負極側循環部導入管１３４は、負極側溶液タンク１３３と負極セル１１４との間に接続された配管である。負極側循環部導入管１３４を用いて、負極側溶液タンク１３３から負極セル１１４に対して、還元された状態の負極活物質１３１を含む負極電解液１３２が導入（供給）される。負極側循環部導出管１３５は、負極セル１１４と負極側溶液タンク１３３との間に接続された配管である。負極側循環部導出管１３５を用いて、負極セル１１４から負極側溶液タンク１３３に対して、酸化された状態の負極活物質１３１を含む負極電解液１３２が導出（排出）される。負極側循環用ポンプ１３６は、例えば負極側循環部導出管１３５に接続された送液用のポンプである。負極側循環用ポンプ１３６を用いて、負極側溶液タンク１３３と負極セル１１４との間において、負極活物質１３１を含む負極電解液１３２を循環させる。 The negative electrode side circulation portion introduction pipe 134 is a pipe connected between the negative electrode side solution tank 133 and the negative electrode cell 114. A negative electrode electrolytic solution 132 containing a reduced negative electrode active material 131 is introduced (supplied) from the negative electrode side solution tank 133 to the negative electrode cell 114 by using the negative electrode side circulation portion introduction tube 134. The negative electrode side circulation portion lead-out pipe 135 is a pipe connected between the negative electrode cell 114 and the negative electrode side solution tank 133. The negative electrode electrolytic solution 132 containing the oxidized negative electrode active material 131 is led out (discharged) from the negative electrode cell 114 to the negative electrode side solution tank 133 by using the negative electrode side circulation unit lead-out tube 135. The negative electrode side circulation pump 136 is, for example, a pump for feeding liquid connected to the negative electrode side circulation portion lead-out pipe 135. The negative electrode side circulation pump 136 is used to circulate the negative electrode electrolytic solution 132 containing the negative electrode active material 131 between the negative electrode side solution tank 133 and the negative electrode cell 114.

「酸化部１４０の構成」
酸化部１４０は、酸化部材（酸化剤１４１）を収容する酸化部材収容部（正極側充電タンク１４２）を有し、正極電解液１２２を該正極側充電タンク１４２へ流通させる。換言すると、酸化部１４０は、正極電解液１２２に含まれる正極活物質１２１を酸化させる。酸化部１４０は、図２に示すように、酸化剤１４１と、正極側充電タンク１４２（酸化剤タンク）と、酸化部導入管１４３と、酸化部導入弁１４４と、酸化部導出管１４５と、酸化部導出弁１４６と、正極側酸化用ポンプ１４７と、を有している。 "Structure of oxidized portion 140"
The oxidizing unit 140 has an oxidizing member accommodating unit (positive electrode side charging tank 142) for accommodating the oxidizing member (oxidizing agent 141), and the positive electrode electrolytic solution 122 is circulated to the positive electrode side charging tank 142. In other words, the oxidizing unit 140 oxidizes the positive electrode active material 121 contained in the positive electrode electrolytic solution 122. As shown in FIG. 2, the oxidized portion 140 includes an oxidizing agent 141, a positive charge side charging tank 142 (oxidizing agent tank), an oxidizing portion introduction tube 143, an oxidizing portion introduction valve 144, and an oxidizing portion outlet tube 145. It has an oxide part lead-out valve 146 and a positive electrode side oxidation pump 147.

酸化剤１４１は、正極活物質１２１を酸化反応させる。酸化剤１４１には、例えば、ＦｅＰＯ４、Ｍｎ２Ｏ４又はＮｉ０．５Ｍｎ１．５Ｏ４が用いられる。酸化剤１４１は、粉状の状態のままで、正極側充電タンク１４２に充填する場合、正極側充電タンク１４２と酸化部導入管１４３との接続部分、及び正極側充電タンク１４２と酸化部導出管１４５との接続部分に、それぞれフィルタを備えた構成とすることができる。フィルタは、酸化剤１４１を通さず、正極活物質１２１を含む正極電解液１２２を通す構成のものが用いられる。 The oxidant 141 causes an oxidation reaction of the positive electrode active material 121. As the oxidizing agent 141, for example, FePO 4 , Mn 2 O 4 or Ni 0.5 Mn 1.5 O 4 is used. When the oxidizing agent 141 is filled in the positive electrode side charging tank 142 in a powdery state, the connecting portion between the positive electrode side charging tank 142 and the oxidizing portion introduction pipe 143, and the positive electrode side charging tank 142 and the oxidizing portion outlet pipe are used. A filter may be provided at each connection portion with the 145. As the filter, one having a structure in which the positive electrode electrolytic solution 122 containing the positive electrode active material 121 is passed without passing through the oxidizing agent 141 is used.

酸化剤１４１は、上記の構成に限定されることなく、例えば、円柱形状に固形化した構成としてもよい。固形化された酸化剤１４１は、正極活物質１２１を含む正極電解液１２２が通過可能な孔を備える。このような構成とした場合、固形化された酸化剤１４１は、正極活物質１２１を含む正極電解液１２２が通過する場合に、溶出せずに、その形状の大部分が維持されればよい。 The oxidizing agent 141 is not limited to the above configuration, and may be solidified into a cylindrical shape, for example. The solidified oxidizing agent 141 has a hole through which the positive electrode electrolytic solution 122 containing the positive electrode active material 121 can pass. With such a configuration, the solidified oxidant 141 does not elute when the positive electrode electrolytic solution 122 containing the positive electrode active material 121 passes through, and most of its shape may be maintained.

酸化剤１４１は、正極側充電タンク１４２に対して交換可能（再充填可能）に構成されている。すなわち、酸化剤１４１は、正極側充電タンク１４２が設けられた車両１０に対して交換可能に構成されている。また、酸化剤１４１は、固形化して構成した場合、正極側充電タンク１４２に対して複数個、設けることができる。この場合、複数個の固形化された酸化剤１４１は、正極側充電タンク１４２に対して選択的に補充可能（任意の固形化された酸化剤１４１を選択して着脱可能）に構成することもできる。 The oxidant 141 is configured to be replaceable (refillable) with respect to the positive electrode side charging tank 142. That is, the oxidizing agent 141 is configured to be replaceable with respect to the vehicle 10 provided with the positive electrode side charging tank 142. Further, when the oxidizing agent 141 is solidified, a plurality of oxidizing agents 141 can be provided to the positive electrode side charging tank 142. In this case, the plurality of solidified oxidants 141 may be selectively replenished to the positive electrode side charging tank 142 (any solidified oxidant 141 may be selected and detached). can.

正極側充電タンク１４２は、酸化剤１４１を収容する容器である。正極側充電タンク１４２は、正極側溶液タンク１２３に対して並列に接続されている。正極側充電タンク１４２は、例えば、１つから構成され、車両１０の後方のトランクの部分などに設ける。正極側充電タンク１４２は、車両１０に対して交換可能（着脱可能）に構成されている。正極側充電タンク１４２は、例えば、負極側充電タンク１５２と水平方向に並べて設けることができる。また、正極側充電タンク１４２は、例えば、負極側充電タンク１５２よりも交換頻度が高い場合、負極側充電タンク１５２の上方に位置するように、負極側充電タンク１５２と垂直方向に並べて設けることができる。正極側充電タンク１４２は、複数本から構成することもできる。この場合、複数本の正極側充電タンク１４２を、例えば、酸化部１４０の配管に対して並列接続又は直列接続することによって、車両１０に対して選択的に補充可能（複数本のうち任意の正極側充電タンク１４２を着脱可能）に構成することもできる。 The positive electrode side charging tank 142 is a container for accommodating the oxidizing agent 141. The positive electrode side charging tank 142 is connected in parallel to the positive electrode side solution tank 123. The positive electrode side charging tank 142 is composed of, for example, one, and is provided in a trunk portion at the rear of the vehicle 10. The positive electrode side charging tank 142 is configured to be replaceable (detachable) with respect to the vehicle 10. The positive electrode side charging tank 142 can be provided side by side with the negative electrode side charging tank 152, for example. Further, for example, when the positive electrode side charging tank 142 is replaced more frequently than the negative electrode side charging tank 152, the positive electrode side charging tank 142 may be provided side by side with the negative electrode side charging tank 152 so as to be located above the negative electrode side charging tank 152. can. The positive electrode side charging tank 142 may be composed of a plurality of the charging tanks 142. In this case, a plurality of positive electrode side charging tanks 142 can be selectively replenished to the vehicle 10 by, for example, connecting in parallel or in series to the piping of the oxidizing portion 140 (any positive electrode among the plurality of positive electrodes). The side charging tank 142 can also be attached and detached).

酸化部導入管１４３は、正極側充電タンク１４２と正極側溶液タンク１２３との間に接続された配管である。酸化部導入管１４３を用いて、正極側充電タンク１４２から正極側溶液タンク１２３に対して、正極活物質１２１を含む正極電解液１２２を流通（供給）させる。酸化部導入弁１４４は、例えば、流体用の電磁弁であり、酸化部導入管１４３に接続されている。酸化部導入弁１４４を用いて、正極側充電タンク１４２から正極側溶液タンク１２３に対する、正極活物質１２１を含む正極電解液１２２の流通（供給）を制御する。酸化部導入弁１４４は、酸化部導出弁１４６と共に、正極電解液１２２の正極側充電タンク１４２への流通状態を調整する第１流通状態調整部に含まれている。酸化部導入弁１４４は、正極側充電タンク１４２の上流側に設けられた正極側開閉弁に相当する。 The oxide part introduction pipe 143 is a pipe connected between the positive electrode side charging tank 142 and the positive electrode side solution tank 123. The positive electrode electrolytic solution 122 containing the positive electrode active material 121 is circulated (supplied) from the positive electrode side charging tank 142 to the positive electrode side solution tank 123 using the oxide part introduction pipe 143. The oxide part introduction valve 144 is, for example, an electromagnetic valve for a fluid, and is connected to the oxide part introduction pipe 143. The oxide part introduction valve 144 is used to control the flow (supply) of the positive electrode electrolyte 122 containing the positive electrode active material 121 from the positive electrode side charging tank 142 to the positive electrode side solution tank 123. The oxide unit introduction valve 144 is included in the first distribution state adjusting unit that adjusts the distribution state of the positive electrode electrolytic solution 122 to the positive electrode side charging tank 142 together with the oxide unit lead-out valve 146. The oxide part introduction valve 144 corresponds to a positive electrode side on-off valve provided on the upstream side of the positive electrode side charging tank 142.

酸化部導出管１４５は、正極側溶液タンク１２３と正極側充電タンク１４２との間に接続された配管である。酸化部導出管１４５を用いて、正極側溶液タンク１２３から正極側充電タンク１４２に対して、正極活物質１２１を含む正極電解液１２２を流通（排出）させる。酸化部導出弁１４６は、例えば、流体用の電磁弁であり、酸化部導出管１４５に接続されている。酸化部導出弁１４６を用いて、正極側溶液タンク１２３から正極側充電タンク１４２に対する、正極活物質１２１を含む正極電解液１２２の流通（供給）を制御する。酸化部導出弁１４６は、正極側充電タンク１４２の下流側に設けられた正極側開閉弁に相当する。正極側酸化用ポンプ１４７は、例えば、送液用のポンプであり、酸化部導出管１４５に接続されている。正極側酸化用ポンプ１４７を用いて、正極側充電タンク１４２と正極側溶液タンク１２３との間において、正極活物質１２１を含む正極電解液１２２を流通させる。 The oxide part lead-out pipe 145 is a pipe connected between the positive electrode side solution tank 123 and the positive electrode side charging tank 142. The positive electrode electrolytic solution 122 containing the positive electrode active material 121 is circulated (discharged) from the positive electrode side solution tank 123 to the positive electrode side charging tank 142 by using the oxidized portion lead-out tube 145. The oxide part lead-out valve 146 is, for example, an electromagnetic valve for a fluid, and is connected to the oxide part lead-out tube 145. The oxide part lead-out valve 146 is used to control the flow (supply) of the positive electrode electrolyte 122 containing the positive electrode active material 121 from the positive electrode side solution tank 123 to the positive electrode side charging tank 142. The oxide part lead-out valve 146 corresponds to a positive electrode side on-off valve provided on the downstream side of the positive electrode side charging tank 142. The positive electrode side oxidation pump 147 is, for example, a pump for feeding liquid, and is connected to the oxide unit lead-out pipe 145. Using the positive electrode side oxidation pump 147, the positive electrode electrolytic solution 122 containing the positive electrode active material 121 is circulated between the positive electrode side charging tank 142 and the positive electrode side solution tank 123.

「還元部１５０の構成」
還元部１５０は、還元部材（還元剤１５１）を収容する還元部材収容部（負極側充電タンク１５２）を有し、負極電解液１３２を該負極側充電タンク１５２へ流通させる。換言すると、還元部１５０は、負極電解液１３２に含まれる負極活物質１３１を還元させる。還元部１５０は、図２に示すように、還元剤１５１と、負極側充電タンク１５２と、還元部導入管１５３と、還元部導入弁１５４と、還元部導出管１５５と、還元部導出弁１５６と、負極側還元用ポンプ１５７と、を有している。 "Structure of reduction unit 150"
The reducing unit 150 has a reducing member accommodating unit (negative electrode side charging tank 152) accommodating a reducing member (reducing agent 151), and distributes the negative electrode electrolytic solution 132 to the negative electrode side charging tank 152. In other words, the reducing unit 150 reduces the negative electrode active material 131 contained in the negative electrode electrolytic solution 132. As shown in FIG. 2, the reducing unit 150 includes a reducing agent 151, a negative electrode side charging tank 152, a reducing unit introduction pipe 153, a reducing unit introduction valve 154, a reducing unit outlet pipe 155, and a reducing unit outlet valve 156. And a negative electrode side reduction pump 157.

還元剤１５１は、負極活物質１３１を還元反応させる。還元剤１５１には、例えば、Ｌｉ７Ｔｉ５Ｏ１２、Ｌｉ－Ｓｉ合金又はＬｉ金属が用いられる。還元剤１５１は、粉状の状態のままで、負極側充電タンク１５２に充填する場合、負極側充電タンク１５２と還元部導入管１５３との接続部分、及び負極側充電タンク１５２と還元部導出管１５５との接続部分に、それぞれフィルタを備えた構成とすることができる。フィルタは、還元剤１５１を通さず、負極活物質１３１を含む負極電解液１３２を通す構成のものが用いられる。 The reducing agent 151 causes the negative electrode active material 131 to undergo a reducing reaction. As the reducing agent 151, for example, Li 7 Ti 5 O 12 , Li—Si alloy or Li metal is used. When the reducing agent 151 is filled in the negative electrode side charging tank 152 in a powdery state, the connecting portion between the negative electrode side charging tank 152 and the reducing portion introduction pipe 153, and the negative electrode side charging tank 152 and the reducing portion lead-out pipe are used. A filter may be provided at each connection portion with the 155. As the filter, one having a structure in which the negative electrode electrolytic solution 132 containing the negative electrode active material 131 is passed without passing through the reducing agent 151 is used.

還元剤１５１は、上記の構成に限定されることなく、例えば、円柱形状に固形化した構成としてもよい。固形化された還元剤１５１は、負極活物質１３１を含む負極電解液１３２が通過可能な孔を備える。このような構成とした場合、固形化された還元剤１５１は、負極活物質１３１を含む負極電解液１３２が通過する場合に、溶出せずに、その形状の大部分が維持されればよい。 The reducing agent 151 is not limited to the above configuration, and may be solidified into a cylindrical shape, for example. The solidified reducing agent 151 has a hole through which the negative electrode electrolytic solution 132 containing the negative electrode active material 131 can pass. With such a configuration, the solidified reducing agent 151 does not elute when the negative electrode electrolytic solution 132 containing the negative electrode active material 131 passes through, and most of its shape may be maintained.

還元剤１５１は、負極側充電タンク１５２に対して交換可能（再充填可能）に構成されている。すなわち、還元剤１５１は、負極側充電タンク１５２が設けられた車両１０に対して交換可能に構成されている。また、還元剤１５１は、固形化して構成した場合、負極側充電タンク１５２に対して複数個、設けることができる。この場合、複数個の固形化された還元剤１５１は、負極側充電タンク１５２に対して選択的に補充可能（任意の固形化された還元剤１５１を選択して着脱可能）に構成することもできる。 The reducing agent 151 is configured to be replaceable (refillable) with respect to the negative electrode side charging tank 152. That is, the reducing agent 151 is configured to be replaceable with respect to the vehicle 10 provided with the negative electrode side charging tank 152. Further, when the reducing agent 151 is solidified, a plurality of reducing agents 151 can be provided for the negative electrode side charging tank 152. In this case, the plurality of solidified reducing agents 151 may be configured to be selectively replenishable to the negative electrode side charging tank 152 (removable by selecting an arbitrary solidified reducing agent 151). can.

負極側充電タンク１５２は、還元剤１５１を収容する容器である。負極側充電タンク１５２は、負極側溶液タンク１３３に対して並列に接続されている。負極側充電タンク１５２は、例えば、１つから構成され、車両１０の後方のトランクの部分などに設ける。負極側充電タンク１５２は、車両１０に対して交換可能（着脱可能）に構成されている。負極側充電タンク１５２は、複数本から構成することもできる。この場合、複数本の負極側充電タンク１５２を、例えば、還元部１５０の配管に対して並列接続又は直列接続することによって、車両１０に対して選択的に補充可能（複数本のうち任意の負極側充電タンク１５２を着脱可能）に構成することもできる。 The negative electrode side charging tank 152 is a container for accommodating the reducing agent 151. The negative electrode side charging tank 152 is connected in parallel to the negative electrode side solution tank 133. The negative electrode side charging tank 152 is composed of, for example, one, and is provided in a trunk portion at the rear of the vehicle 10. The negative electrode side charging tank 152 is configured to be replaceable (detachable) with respect to the vehicle 10. The negative electrode side charging tank 152 may be composed of a plurality of the charging tanks 152. In this case, a plurality of negative electrode side charging tanks 152 can be selectively replenished to the vehicle 10 by, for example, connecting in parallel or in series to the piping of the reduction unit 150 (any negative electrode among the plurality of negative electrodes). The side charging tank 152 can also be attached and detached).

還元部導入管１５３は、負極側充電タンク１５２と負極側溶液タンク１３３との間に接続された配管である。還元部導入管１５３を用いて、負極側充電タンク１５２から負極側溶液タンク１３３に対して、負極活物質１３１を含む負極電解液１３２を流通（供給）させる。還元部導入弁１５４は、例えば、流体用の電磁弁であり、還元部導入管１５３に接続されている。還元部導入弁１５４を用いて、負極側充電タンク１５２から負極側溶液タンク１３３に対する、負極活物質１３１を含む負極電解液１３２の流通（供給）を制御する。還元部導入弁１５４は、還元部導出弁１５６と共に、負極電解液１３２の負極側充電タンク１５２への流通状態を調整する第２流通状態調整部を構成している。還元部導入弁１５４は、負極側充電タンク１５２の上流側に設けられた負極側開閉弁に相当する。 The reduction section introduction pipe 153 is a pipe connected between the negative electrode side charging tank 152 and the negative electrode side solution tank 133. The negative electrode electrolytic solution 132 containing the negative electrode active material 131 is circulated (supplied) from the negative electrode side charging tank 152 to the negative electrode side solution tank 133 using the reduction section introduction pipe 153. The reduction section introduction valve 154 is, for example, a solenoid valve for a fluid, and is connected to the reduction section introduction pipe 153. The reduction section introduction valve 154 is used to control the flow (supply) of the negative electrode electrolyte 132 containing the negative electrode active material 131 from the negative electrode side charging tank 152 to the negative electrode side solution tank 133. The reduction unit introduction valve 154, together with the reduction unit lead-out valve 156, constitutes a second distribution state adjustment unit that adjusts the distribution state of the negative electrode electrolyte 132 to the negative electrode side charging tank 152. The reduction section introduction valve 154 corresponds to a negative electrode side on-off valve provided on the upstream side of the negative electrode side charging tank 152.

還元部導出管１５５は、負極側溶液タンク１３３と負極側充電タンク１５２との間に接続された配管である。還元部導出管１５５を用いて、負極側溶液タンク１３３から負極側充電タンク１５２に対して、負極活物質１３１を含む負極電解液１３２を流通（排出）する。還元部導出弁１５６は、例えば、流体用の電磁弁であり、還元部導出管１５５に接続されている。還元部導出弁１５６を用いて、負極側溶液タンク１３３から負極側充電タンク１５２に対する、負極活物質１３１を含む負極電解液１３２の流通（供給）を制御する。還元部導出弁１５６は、負極側充電タンク１５２の下流側に設けられた負極側開閉弁に相当する。負極側還元用ポンプ１５７は、例えば、送液用のポンプであり、還元部導出管１５５に接続されている。負極側還元用ポンプ１５７を用いて、負極側充電タンク１５２と負極側溶液タンク１３３との間において、負極活物質１３１を含む負極電解液１３２を流通させる。 The reduction section lead-out pipe 155 is a pipe connected between the negative electrode side solution tank 133 and the negative electrode side charging tank 152. The negative electrode electrolytic solution 132 containing the negative electrode active material 131 is circulated (discharged) from the negative electrode side solution tank 133 to the negative electrode side charging tank 152 by using the reduction section lead-out tube 155. The reduction section lead-out valve 156 is, for example, a solenoid valve for a fluid, and is connected to the reduction section lead-out pipe 155. The reduction section lead-out valve 156 is used to control the flow (supply) of the negative electrode electrolyte 132 containing the negative electrode active material 131 from the negative electrode side solution tank 133 to the negative electrode side charging tank 152. The reduction section lead-out valve 156 corresponds to a negative electrode side on-off valve provided on the downstream side of the negative electrode side charging tank 152. The negative electrode side reduction pump 157 is, for example, a liquid feeding pump, and is connected to the reduction unit lead-out pipe 155. Using the negative electrode side reduction pump 157, the negative electrode electrolytic solution 132 containing the negative electrode active material 131 is circulated between the negative electrode side charging tank 152 and the negative electrode side solution tank 133.

「制御部１６０の構成」
制御部１６０は、第１流通状態調整部（酸化部導入弁１４４及び酸化部導出弁１４６）及び第２流通状態調整部（還元部導入弁１５４及び還元部導出弁１５６）を制御する。制御部１６０は、図１等に示すように、車両１０の加速状態を測定する加速センサ１６１ａ（加速状態測定手段）と、正極側及び負極側の充電率を測定する充電センサ１６１ｂ（充電率測定手段）を備えたコントローラ１６１を有している。 "Configuration of control unit 160"
The control unit 160 controls the first distribution state adjusting unit (oxidation unit introduction valve 144 and oxidation unit lead-out valve 146) and the second distribution state adjustment unit (reduction unit introduction valve 154 and reduction unit lead-out valve 156). As shown in FIG. 1, the control unit 160 has an acceleration sensor 161a (acceleration state measuring means) for measuring the acceleration state of the vehicle 10 and a charging sensor 161b (charge rate measurement) for measuring the charge rates on the positive electrode side and the negative electrode side. It has a controller 161 equipped with means).

コントローラ１６１は、加速センサ１６１ａ及び充電センサ１６１ｂ等から得られた情報に基づいて、酸化部導入弁１４４、酸化部導出弁１４６、還元部導入弁１５４及び還元部導出弁１５６等を制御する。コントローラ１６１は、上記の制御のために、ＲＯＭ（Ｒｅａｄ Ｏｎｌｙ Ｍｅｍｏｒｙ）、ＣＰＵ（Ｃｅｎｔｒａｌ Ｐｒｏｃｅｓｓｉｎｇ Ｕｎｉｔ）及びＲＡＭ（Ｒａｎｄｏｍ Ａｃｃｅｓｓ Ｍｅｍｏｒｙ）を有している。ＲＯＭは、車両用フロー電池１００の制御プログラムを格納している。ＣＰＵは、制御プログラムを実行する。ＲＡＭは、ＣＰＵが制御プログラムを実行している間、様々なデータを一時的に記憶する。 The controller 161 controls the oxide part introduction valve 144, the oxide part lead-out valve 146, the reduction part introduction valve 154, the reduction part lead-out valve 156, and the like based on the information obtained from the acceleration sensor 161a, the charge sensor 161b, and the like. The controller 161 has a ROM (Read Only Memory), a CPU (Central Processing Unit), and a RAM (Random Access Memory) for the above control. The ROM stores the control program of the vehicle flow battery 100. The CPU executes the control program. The RAM temporarily stores various data while the CPU is executing the control program.

「電気ユニット２０の構成」
電気ユニット２０は、車両１０に設けられ、車両用フロー電池１００と接続されている。電気ユニット２０は、給電部２１と、インバータ２２と、正極端子２３と、負極端子２４と、駆動機器２５と、を有している。給電部２１は、例えば、車両１０のエンジンであり、発電機として用いる。給電部２１は、車両が駐車される施設に対して電力を送電する発電所や、車両１０が駐車される施設に設けられ電力を生成する発電機器としてもよい。インバータ２２は、給電部２１から車両用フロー電池１００に対して供給される電力を、交流から直流に変換する。また、インバータ２２は、車両用フロー電池１００から駆動機器２５に対して供給される電力を、直流から交流に変換する。正極端子２３は、インバータ２２と発電セル１１０の正極電極１１１とを電気的に接続する。負極端子２４は、インバータ２２と発電セル１１０の負極電極１１３とを電気的に接続する。駆動機器２５は、例えば、車載用モータである。 "Configuration of electric unit 20"
The electric unit 20 is provided in the vehicle 10 and is connected to the vehicle flow battery 100. The electric unit 20 includes a power feeding unit 21, an inverter 22, a positive electrode terminal 23, a negative electrode terminal 24, and a drive device 25. The power feeding unit 21 is, for example, the engine of the vehicle 10 and is used as a generator. The power feeding unit 21 may be a power plant that transmits electric power to a facility where the vehicle is parked, or a power generation device that is provided in the facility where the vehicle 10 is parked and generates electric power. The inverter 22 converts the electric power supplied from the power feeding unit 21 to the vehicle flow battery 100 from alternating current to direct current. Further, the inverter 22 converts the electric power supplied from the vehicle flow battery 100 to the drive device 25 from direct current to alternating current. The positive electrode terminal 23 electrically connects the inverter 22 and the positive electrode 111 of the power generation cell 110. The negative electrode terminal 24 electrically connects the inverter 22 and the negative electrode 113 of the power generation cell 110. The drive device 25 is, for example, an in-vehicle motor.

「車両用フロー電池１００の制御方法」
「基本的な制御方法」
図２及び表１を参照して、車両用フロー電池１００の基本的な制御方法を説明する。 "Control method for vehicle flow battery 100"
"Basic control method"
A basic control method for the vehicle flow battery 100 will be described with reference to FIGS. 2 and 1.

車両用フロー電池１００の基本的な制御方法では、発電セル１１０における充電率の上昇に着目して説明する。特に、発電セル１１０の正極側における充電率の上昇について説明する。負極側の制御は、上記の正極側の制御と同様であることから、説明を省略する。 The basic control method of the vehicle flow battery 100 will be described by focusing on an increase in the charge rate in the power generation cell 110. In particular, an increase in the charge rate on the positive electrode side of the power generation cell 110 will be described. Since the control on the negative electrode side is the same as the control on the positive electrode side, the description thereof will be omitted.

表１に、正極セル１１２、正極側溶液タンク１２３及び正極側充電タンク１４２に関して、体積Ｖ１［ｍ３］、Ｖ２［ｍ３］及びＶ３［ｍ３］を表している。また、表１に、正極セル１１２、正極側溶液タンク１２３及び正極側充電タンク１４２に関して、正極活物質１２１を含む正極電解液１２２の濃度Ｍ１［ｍｏｌ／ｍ３］、Ｍ２［ｍｏｌ／ｍ３］及びＭ３［ｍｏｌ／ｍ３］を表している。また、表１に、正極側溶液タンク１２３から正極セル１１２に対する、及び正極側充電タンク１４２から正極側溶液タンク１２３に対する、正極活物質１２１を含む正極電解液１２２の流量Ｊ１［ｍ３／ｓ］、及びＪ２［ｍ３／ｓ］を表している。 Table 1 shows the volumes V 1 [m 3 ], V 2 [m 3 ], and V 3 [m 3 ] with respect to the positive electrode cell 112, the positive electrode side solution tank 123, and the positive electrode side charging tank 142. Further, in Table 1, with respect to the positive electrode cell 112, the positive electrode side solution tank 123, and the positive electrode side charging tank 142, the concentrations of the positive electrode electrolyte 122 containing the positive electrode active material 121 are M 1 [mol / m 3 ] and M 2 [mol / m]. 3 ] and M 3 [mol / m 3 ] are represented. Further, in Table 1, the flow rate J 1 [m 3 / s of the positive electrode electrolytic solution 122 containing the positive electrode active material 121 from the positive electrode side solution tank 123 to the positive electrode cell 112 and from the positive electrode side charging tank 142 to the positive electrode side solution tank 123. ], And J 2 [m 3 / s].

Figure 0007091934000001
Figure 0007091934000001

正極セル１１２に循環させる正極活物質１２１を含む正極電解液１２２の流量Ｊ１［ｍ３／ｓ］と、酸化剤１４１に流通させる正極活物質１２１を含む正極電解液１２２の流量Ｊ２［ｍ３／ｓ］と関係は、数１に基づいて、数２によって表される。 The flow rate J 1 [m 3 / s] of the positive electrode electrolyte 122 containing the positive electrode active material 121 circulated in the positive electrode cell 112 and the flow rate J 2 [m] of the positive electrode electrolyte 122 containing the positive electrode active material 121 circulated in the oxidizing agent 141. 3 / s] and the relationship are represented by the number 2 based on the number 1.

Figure 0007091934000002
Figure 0007091934000002

Figure 0007091934000003
Figure 0007091934000003

ここで、流量Ｊ２［ｍ３／ｓ］を流量Ｊ１［ｍ３／ｓ］に対して増加させることによって、正極側の充電率を上昇させるように制御する。 Here, by increasing the flow rate J 2 [m 3 / s] with respect to the flow rate J 1 [m 3 / s], the charge rate on the positive electrode side is controlled to increase.

「具体的な制御方法１」
図２を参照して、車両１０を長距離にわたり走行させることによって、車両用フロー電池１００の充電率が徐々に低下するような場合に好ましい制御方法１を説明する。 "Specific control method 1"
With reference to FIG. 2, a control method 1 preferable when the charge rate of the vehicle flow battery 100 gradually decreases due to the vehicle 10 traveling over a long distance will be described.

このような制御は、例えば、車両１０を走行中に充電する施設が無い場合、車両１０を充電する施設が有っても混雑している場合、及び車両１０の走行を長距離にわたって継続したい場合を想定している。なお、車両１０を長距離にわたって継続して走行させる場合、例えば自動運転であれば、運転の疲れによる影響を考慮する必要がない。 Such control is performed, for example, when there is no facility for charging the vehicle 10 while traveling, when the facility is crowded even if there is a facility for charging the vehicle 10, and when the vehicle 10 is desired to continue traveling for a long distance. Is assumed. When the vehicle 10 is continuously driven over a long distance, for example, in the case of automatic driving, it is not necessary to consider the influence of driving fatigue.

正極側の充電率は、次のようにして算出する。すなわち、正極側の充電率は、正極側溶液タンク１２３に収容された正極活物質１２１を含む正極電解液１２２の電圧、又は正極側循環部導出管１２５を流れる正極活物質１２１を含む正極電解液１２２の電圧を、一定時間ごとに充電センサ１６１ｂから算出する。 The charge rate on the positive electrode side is calculated as follows. That is, the charge rate on the positive electrode side is the voltage of the positive electrode electrolytic solution 122 containing the positive electrode active material 121 housed in the positive electrode side solution tank 123, or the positive electrode electrolytic solution containing the positive electrode active material 121 flowing through the positive electrode side circulation portion lead-out tube 125. The voltage of 122 is calculated from the charge sensor 161b at regular intervals.

正極側の充電率が所定の値未満となった場合に、正極側溶液タンク１２３に収容された正極活物質１２１を含む正極電解液１２２を、正極側充電タンク１４２に収容された酸化剤１４１に対して、正極側酸化用ポンプ１４７を運転させて送液する。正極側の充電率に関する所定の値は、例えば３０％のように予め設定するが、車両１０の運転者などが随時変更可能な構成としてもよい。 When the charge rate on the positive electrode side becomes less than a predetermined value, the positive electrode electrolytic solution 122 containing the positive electrode active material 121 contained in the positive electrode side solution tank 123 is added to the oxidizing agent 141 contained in the positive electrode side charging tank 142. On the other hand, the positive electrode side oxidation pump 147 is operated to feed the liquid. The predetermined value regarding the charge rate on the positive electrode side is set in advance, for example, 30%, but may be configured so that the driver of the vehicle 10 or the like can change it at any time.

正極側の充電率が設定値（例えば５０％）まで上昇した場合、正極側酸化用ポンプ１４７の運転を止めて、正極側溶液タンク１２３から正極側充電タンク１４２に対する、正極活物質１２１を含む正極活物質１２１の流通を停止する。 When the charge rate on the positive electrode side rises to a set value (for example, 50%), the operation of the positive electrode side oxidation pump 147 is stopped, and the positive electrode containing the positive electrode active material 121 from the positive electrode side solution tank 123 to the positive electrode side charging tank 142. Stop the distribution of the active material 121.

負極側の充電率は、次のようにして算出する。すなわち、負極側の充電率は、負極側溶液タンク１３３に収容された負極活物質１３１を含む負極電解液１３２の電圧、又は負極側循環部導出管１３５を流れる負極活物質１３１を含む負極電解液１３２の電圧を、一定時間ごとに充電センサ１６１ｂから算出する。 The charge rate on the negative electrode side is calculated as follows. That is, the charge rate on the negative electrode side is the voltage of the negative electrode electrolytic solution 132 containing the negative electrode active material 131 housed in the negative electrode side solution tank 133, or the negative electrode electrolytic solution containing the negative electrode active material 131 flowing through the negative electrode side circulation portion lead-out tube 135. The voltage of 132 is calculated from the charge sensor 161b at regular intervals.

負極側の充電率が所定の値未満となった場合に、負極側溶液タンク１３３に収容された負極活物質１３１を含む負極電解液１３２を、負極側充電タンク１５２に収容された還元剤１５１に対して、負極側還元用ポンプ１５７を運転させて送液する。負極側の充電率に関する所定の値は、例えば３０％のように予め設定するが、車両１０の運転者などが随時変更可能な構成としてもよい。負極側の充電率に関する所定の値は、正極側の充電率に関する所定の値と異ならせてもよい。 When the charge rate on the negative electrode side becomes less than a predetermined value, the negative electrode electrolytic solution 132 containing the negative electrode active material 131 contained in the negative electrode side solution tank 133 is added to the reducing agent 151 contained in the negative electrode side charging tank 152. On the other hand, the negative electrode side reduction pump 157 is operated to feed the liquid. The predetermined value regarding the charge rate on the negative electrode side is set in advance, for example, 30%, but may be configured so that the driver of the vehicle 10 or the like can change it at any time. The predetermined value regarding the charge rate on the negative electrode side may be different from the predetermined value regarding the charge rate on the positive electrode side.

負極側の充電率が設定値（例えば５０％）まで上昇した場合、負極側還元用ポンプ１５７の運転を止めて、負極側溶液タンク１３３から負極側充電タンク１５２に対する、負極活物質１３１を含む負極活物質１３１の流通を停止する。 When the charge rate on the negative electrode side rises to a set value (for example, 50%), the operation of the negative electrode side reduction pump 157 is stopped, and the negative electrode containing the negative electrode active material 131 from the negative electrode side solution tank 133 to the negative electrode side charging tank 152. Stop the distribution of the active material 131.

「具体的な制御方法２」
図２を参照して、車両１０に高負荷が発生することによって、車両用フロー電池１００の充電率が急減するような場合に好ましい制御方法２を説明する。 "Specific control method 2"
With reference to FIG. 2, a control method 2 preferable when the charge rate of the vehicle flow battery 100 suddenly decreases due to a high load generated on the vehicle 10 will be described.

このような制御は、例えば、車両１０が勾配の大きい坂道を走行する場合、車両１０が重量物を積載又は牽引して走行する場合、高速走行する場合、及び車両１０に設けた空調機器を最大で動作させる場合（例えば炎天下で駐車していた状態から急速に空冷しつつ走行する場合）を想定している。 Such control is performed, for example, when the vehicle 10 travels on a slope with a large slope, when the vehicle 10 loads or tows a heavy object, travels at a high speed, and when the air conditioning device provided in the vehicle 10 is maximized. It is assumed that the vehicle will be operated in (for example, when the vehicle is parked under the scorching sun and then rapidly cooled in the air).

正極側の充電率が単位時間当たりに所定の割合を超えて減少した場合に、正極側溶液タンク１２３に収容された正極活物質１２１を含む正極電解液１２２を、正極側充電タンク１４２に収容された酸化剤１４１に対して、正極側酸化用ポンプ１４７を運転させて送液する。所定の割合は、車両１０を通常の条件で走行させた場合における、正極側溶液タンク１２３での単位時間当たりの充電率の減少率を基準として、その減少率よりも高い値で設定する。すなわち、正極側の充電率が、車両１０を通常の条件で走行させた場合よりも、例えば５倍以上の高い割合で急減した場合に、この制御を実行する。正極側の充電率の算出に関する構成、及び正極側の充電率が設定値（例えば５０％）まで上昇した場合の構成は、制御方法１と同様である。 When the charging rate on the positive electrode side decreases by more than a predetermined ratio per unit time, the positive electrode electrolytic solution 122 containing the positive electrode active material 121 contained in the positive electrode side solution tank 123 is stored in the positive electrode side charging tank 142. The positive electrode side oxidation pump 147 is operated to feed the oxidant 141. The predetermined ratio is set at a value higher than the decrease rate of the charge rate per unit time in the positive electrode side solution tank 123 when the vehicle 10 is run under normal conditions. That is, this control is executed when the charge rate on the positive electrode side suddenly decreases at a rate higher than that when the vehicle 10 is run under normal conditions, for example, by 5 times or more. The configuration for calculating the charge rate on the positive electrode side and the configuration when the charge rate on the positive electrode side rises to a set value (for example, 50%) are the same as those in the control method 1.

負極側の充電率が単位時間当たりに所定の割合を超えて減少した場合に、負極側溶液タンク１３３に収容された負極活物質１３１を含む負極電解液１３２を、負極側充電タンク１５２に収容された還元剤１５１に対して、負極側還元用ポンプ１５７を運転させて送液する。所定の割合は、車両１０を通常の条件で走行させた場合における、負極側溶液タンク１３３での単位時間当たりの充電率の減少率を基準として、その減少率よりも高い値で設定する。すなわち、負極側の充電率が、車両１０を通常の条件で走行させた場合よりも、例えば５倍以上の高い割合で急減した場合に、この制御を実行する。負極側の充電率の算出に関する構成、及び負極側の充電率が設定値（例えば５０％）まで上昇した場合の構成は、制御方法１と同様である。 When the charging rate on the negative electrode side decreases by more than a predetermined ratio per unit time, the negative electrode electrolytic solution 132 containing the negative electrode active material 131 contained in the negative electrode side solution tank 133 is stored in the negative electrode side charging tank 152. The negative electrode side reducing pump 157 is operated to send the liquid to the reducing agent 151. The predetermined ratio is set at a value higher than the decrease rate of the charge rate per unit time in the negative electrode side solution tank 133 when the vehicle 10 is run under normal conditions. That is, this control is executed when the charge rate on the negative electrode side suddenly decreases at a rate higher than that when the vehicle 10 is run under normal conditions, for example, by 5 times or more. The configuration for calculating the charge rate on the negative electrode side and the configuration when the charge rate on the negative electrode side rises to a set value (for example, 50%) are the same as those in the control method 1.

「具体的な制御方法３」
図２を参照して、車両１０を走行状態に依存することなく、車両用フロー電池１００の充電率を定の値（例えば３０％）以上に維持する必要がある場合に好ましい制御方法３を説明する。 "Specific control method 3"
With reference to FIG. 2, a control method 3 preferable when it is necessary to maintain the charge rate of the vehicle flow battery 100 at a constant value (for example, 30%) or more without depending on the traveling state of the vehicle 10 will be described. do.

このような制御は、例えば、タクシーのように車両１０の走行の予測を立て難い場合、及び消防車のような緊急用車両において走行に一定の余裕を保つ必要がある場合を想定している。 Such control assumes, for example, a case where it is difficult to predict the traveling of the vehicle 10 such as a taxi, and a case where it is necessary to maintain a certain margin for traveling in an emergency vehicle such as a fire engine.

正極側の充電率が所定の値以上になるように、正極側溶液タンク１２３に収容された正極活物質１２１を含む正極電解液１２２を、正極側充電タンク１４２に収容された酸化剤１４１に対して、正極側酸化用ポンプ１４７の出力を可変しながら運転させて送液する。このような制御によって、酸化剤１４１に対する正極電解液１２２の流量を調整（増加又は減少）する。酸化剤１４１に対する正極電解液１２２の流量の調整は、正極側酸化用ポンプ１４７の出力を可変する制御に限定されることなく、正極側酸化用ポンプ１４７の出力を一定にして酸化部導入弁１４４又は酸化部導出弁１４６の開度を可変させる制御によって実行してもよい。正極側の充電率の算出に関する構成は、制御方法１と同様である。 The positive electrode electrolytic solution 122 containing the positive electrode active material 121 contained in the positive electrode side solution tank 123 is applied to the oxidizing agent 141 contained in the positive electrode side charging tank 142 so that the charging rate on the positive electrode side becomes equal to or higher than a predetermined value. Then, the liquid is sent by operating while changing the output of the positive electrode side oxidation pump 147. By such control, the flow rate of the positive electrode electrolyte 122 with respect to the oxidizing agent 141 is adjusted (increased or decreased). The adjustment of the flow rate of the positive electrode electrolyte 122 with respect to the oxidant 141 is not limited to the control of varying the output of the positive electrode side oxidizing pump 147, but the output of the positive electrode side oxidizing pump 147 is kept constant and the oxide part introduction valve 144 is used. Alternatively, it may be executed by controlling to change the opening degree of the oxide part lead-out valve 146. The configuration for calculating the charge rate on the positive electrode side is the same as that of the control method 1.

負極側の充電率が所定の値以上になるように、負極側溶液タンク１３３に収容された負極活物質１３１を含む負極電解液１３２を、負極側充電タンク１５２に収容された還元剤１５１に対して、負極側還元用ポンプ１５７の出力を可変しながら運転させて送液する。このような制御によって、還元剤１５１に対する負極電解液１３２の流量を調整（増加又は減少）する。還元剤１５１に対する負極電解液１３２の流量の調整は、負極側還元用ポンプ１５７の出力を可変する制御に限定されることなく、負極側還元用ポンプ１５７の出力を一定にして還元部導入弁１５４又は還元部導出弁１５６の開度を可変させる制御によって実行してもよい。負極側の充電率の算出に関する構成は、制御方法１と同様である。 The negative electrode electrolytic solution 132 containing the negative electrode active material 131 contained in the negative electrode side solution tank 133 is applied to the reducing agent 151 contained in the negative electrode side charging tank 152 so that the charging rate on the negative electrode side becomes equal to or higher than a predetermined value. Then, the negative electrode side reduction pump 157 is operated while varying the output to feed the liquid. By such control, the flow rate of the negative electrode electrolyte 132 with respect to the reducing agent 151 is adjusted (increased or decreased). The adjustment of the flow rate of the negative electrode electrolyte 132 with respect to the reducing agent 151 is not limited to the control of changing the output of the negative electrode side reducing pump 157, and the output of the negative electrode side reducing pump 157 is kept constant to reduce the reduction unit introduction valve 154. Alternatively, it may be executed by controlling to change the opening degree of the reducing unit lead-out valve 156. The configuration for calculating the charge rate on the negative electrode side is the same as that of the control method 1.

「車両用フロー電池１００及びその制御方法の効果」
車両用フロー電池１００及びその制御方法の効果を説明する。 "Effects of Vehicle Flow Battery 100 and Its Control Method"
The effect of the vehicle flow battery 100 and its control method will be described.

第１実施形態によれば、正極活物質１２１を含む正極電解液１２２を、第１流通状態調整部（酸化部導入弁１４４及び酸化部導出弁１４６）によって調整しながら、酸化剤１４１を収容する正極側充電タンク１４２へ流通させる。又、負極活物質１３１を含む負極電解液１３２を、第２流通状態調整部（還元部導入弁１５４及び還元部導出弁１５６）によって調整しながら、還元剤１５１を収容する負極側充電タンク１５２へ流通させる。 According to the first embodiment, the positive electrode electrolytic solution 122 containing the positive electrode active material 121 is adjusted by the first flow state adjusting unit (oxidizing part introduction valve 144 and oxidizing part out-out valve 146) while accommodating the oxidizing agent 141. It is distributed to the positive electrode side charging tank 142. Further, the negative electrode electrolytic solution 132 containing the negative electrode active material 131 is adjusted by the second flow state adjusting unit (reducing unit introduction valve 154 and reducing unit lead-out valve 156) to the negative electrode side charging tank 152 accommodating the reducing agent 151. Distribute.

このような構成及び制御によれば、正極セル１１２において還元された正極活物質１２１を酸化させる必要がある時には、第１流通状態調整部（酸化部導入弁１４４及び酸化部導出弁１４６）を調整し、酸化剤１４１を収容する正極側充電タンク１４２へ流通させ、酸化剤１４１によって正極活物質１２１を酸化させることができる。また、負極セル１１４において酸化された負極活物質１３１を還元させる必要がある時には、第２流通状態調整部（還元部導入弁１５４及び還元部導出弁１５６）を調整し、還元剤１５１を収容する負極側充電タンク１５２へ流通させ、還元剤１５１によって負極活物質１３１を還元させることができる。さらに、正極セル１１２において還元された正極活物質１２１を酸化させる必要がない時には、第１流通状態調整部（酸化部導入弁１４４及び酸化部導出弁１４６）を調整し、酸化剤１４１を収容する正極側充電タンク１４２への流通を減らすもしくは止めることにより、酸化剤１４１のエネルギーの無駄な消耗を防ぐことができる。また、負極セル１１４において酸化された負極活物質１３１を還元させる必要がない時には、第２流通状態調整部（還元部導入弁１５４及び還元部導出弁１５６）を調整し、還元剤１５１を収容する負極側充電タンク１５２への流通を減らすもしくは止めることにより、還元剤１５１のエネルギーの無駄な消耗を防ぐことができる。ここで、正極活物質１２１を酸化させることによってエネルギーが消耗した酸化剤１４１は溶出せずに固体状態を維持しており、正極活物質１２１を含んだ正極電解液１２２から回収する必要が無い。また、負極活物質１３１を還元させることによってエネルギーが消耗した還元剤１５１は溶出せずに固体状態を維持しており、負極活物質１３１を含んだ負極電解液１３２から回収する必要が無い。これにより、正極側充電タンク１４２及び負極側充電タンク１５２の交換頻度を減らすことができる。この結果、車両用フロー電池１００及びその制御方法は、電解液を交換することなく、車両１０の走行距離を効率良く伸ばすことができ、充電タンクの交換頻度を減らすことができる。 According to such a configuration and control, when it is necessary to oxidize the reduced positive electrode active material 121 in the positive electrode cell 112, the first distribution state adjusting section (oxidizing section introduction valve 144 and oxidizing section lead-out valve 146) is adjusted. Then, it can be distributed to the positive electrode side charging tank 142 containing the oxidizing agent 141, and the positive electrode active material 121 can be oxidized by the oxidizing agent 141. When it is necessary to reduce the oxidized negative electrode active material 131 in the negative electrode cell 114, the second distribution state adjusting unit (reducing unit introduction valve 154 and reducing unit lead-out valve 156) is adjusted to accommodate the reducing agent 151. It can be distributed to the negative electrode side charging tank 152 and the negative electrode active material 131 can be reduced by the reducing agent 151. Further, when it is not necessary to oxidize the reduced positive electrode active material 121 in the positive electrode cell 112, the first flow state adjusting section (oxidizing section introduction valve 144 and oxidizing section lead-out valve 146) is adjusted to accommodate the oxidizing agent 141. By reducing or stopping the distribution to the positive electrode side charging tank 142, it is possible to prevent wasteful consumption of the energy of the oxidizing agent 141. When it is not necessary to reduce the oxidized negative electrode active material 131 in the negative electrode cell 114, the second distribution state adjusting section (reducing section introduction valve 154 and reducing section lead-out valve 156) is adjusted to accommodate the reducing agent 151. By reducing or stopping the distribution to the negative electrode side charging tank 152, it is possible to prevent wasteful consumption of the energy of the reducing agent 151. Here, the oxidant 141 whose energy is consumed by oxidizing the positive electrode active material 121 is maintained in a solid state without being eluted, and it is not necessary to recover the oxidant 141 from the positive electrode electrolytic solution 122 containing the positive electrode active material 121. Further, the reducing agent 151 whose energy is consumed by reducing the negative electrode active material 131 is maintained in a solid state without being eluted, and it is not necessary to recover from the negative electrode electrolytic solution 132 containing the negative electrode active material 131. As a result, the frequency of replacement of the positive electrode side charging tank 142 and the negative electrode side charging tank 152 can be reduced. As a result, the vehicle flow battery 100 and its control method can efficiently extend the mileage of the vehicle 10 without exchanging the electrolytic solution, and can reduce the frequency of exchanging the charging tank.

第１実施形態によれば、正極側充電タンク１４２は、正極側溶液タンク１２３に対して並列に接続されている。同様に、負極側充電タンク１５２は、負極側溶液タンク１３３に対して並列に接続されている。 According to the first embodiment, the positive electrode side charging tank 142 is connected in parallel with the positive electrode side solution tank 123. Similarly, the negative electrode side charging tank 152 is connected in parallel to the negative electrode side solution tank 133.

このような構成によれば、非常に簡便であって、かつ、一定の応答性及び精度を満たした上で、正極活物質１２１を含む正極電解液１２２を、酸化剤１４１を収容する正極側充電タンク１４２へ流通させることができる。又、負極活物質１３１を含む負極電解液１３２を、還元剤１５１を収容する負極側充電タンク１５２へ流通させることができる。 According to such a configuration, the positive electrode electrolyte 122 containing the positive electrode active material 121 is charged on the positive electrode side containing the oxidizing agent 141 while being very simple and satisfying a certain responsiveness and accuracy. It can be distributed to the tank 142. Further, the negative electrode electrolytic solution 132 containing the negative electrode active material 131 can be circulated to the negative electrode side charging tank 152 containing the reducing agent 151.

第１実施形態によれば、正極側充電タンク１４２及び負極側充電タンク１５２が、車両１０に対して、それぞれ交換可能又は補充可能に構成されている。 According to the first embodiment, the positive electrode side charging tank 142 and the negative electrode side charging tank 152 are configured to be replaceable or replenishable with respect to the vehicle 10, respectively.

このような構成によれば、エネルギーを一定以上消耗した酸化剤１４１を収容した正極側充電タンク１４２及びエネルギーを一定以上消耗した還元剤１５１を収容した負極側充電タンク１５２を車両１０から取り外し、十分なエネルギーを備えた酸化剤１４１を収容した正極側充電タンク１４２及び十分なエネルギーを備えた還元剤１５１を収容した負極側充電タンク１５２を車両１０に取り付けるだけで、車両１０の走行距離を伸ばすことができる。すなわち、ガソリンスタンドのような施設において、車両１０を短時間停車させている間に正極側充電タンク１４２及び負極側充電タンク１５２を交換する構成とすれば、車両用フロー電池１００を急速充電可能な二次電池のように扱うことができる。さらに、エネルギーを一定以上消耗した酸化剤１４１を収容した正極側充電タンク１４２又はエネルギーを一定以上消耗した還元剤１５１を収容した負極側充電タンク１５２だけを、選択して交換する構成としてもよい。このような構成とした場合、より短期間で無駄なく正極側充電タンク１４２又は負極側充電タンク１５２の交換を行うことができる。 According to such a configuration, the positive electrode side charging tank 142 containing the oxidizing agent 141 that has consumed more than a certain amount of energy and the negative electrode side charging tank 152 containing the reducing agent 151 that has consumed more than a certain amount of energy can be sufficiently removed from the vehicle 10. By simply attaching the positive electrode side charging tank 142 containing the oxidizing agent 141 having sufficient energy and the negative electrode side charging tank 152 containing the reducing agent 151 having sufficient energy to the vehicle 10, the mileage of the vehicle 10 can be extended. Can be done. That is, in a facility such as a gas station, if the positive electrode side charging tank 142 and the negative electrode side charging tank 152 are replaced while the vehicle 10 is stopped for a short time, the vehicle flow battery 100 can be quickly charged. It can be treated like a secondary battery. Further, only the positive electrode side charging tank 142 containing the oxidizing agent 141 that has consumed energy more than a certain amount or the negative electrode side charging tank 152 containing the reducing agent 151 that has consumed energy more than a certain amount may be selected and replaced. With such a configuration, the positive electrode side charging tank 142 or the negative electrode side charging tank 152 can be replaced in a shorter period of time without waste.

第１実施形態によれば、制御部１６０は、加速センサ１６１ａにより測定される加速度が所定値以上の場合、又は充電センサ１６１ｂにより測定される正極側の充電率が所定の値未満となった場合に、第１流通状態調整部（酸化部導入弁１４４及び酸化部導出弁１４６）により正極電解液１２２を正極側充電タンク１４２へ流通させるように制御する。制御部１６０による負極側の制御は、上記の正極側の制御と同様である。 According to the first embodiment, the control unit 160 has a case where the acceleration measured by the acceleration sensor 161a is equal to or more than a predetermined value, or a case where the charging rate on the positive electrode side measured by the charging sensor 161b is less than a predetermined value. In addition, the positive electrode electrolytic solution 122 is controlled to be circulated to the positive electrode side charging tank 142 by the first flow state adjusting unit (oxidation unit introduction valve 144 and oxidation unit lead-out valve 146). The control on the negative electrode side by the control unit 160 is the same as the control on the positive electrode side described above.

このような制御方法（上記した具体的な制御方法１に相当）によれば、例えば、車両１０を長距離にわたり走行させるような場合に、車両用フロー電池１００の充電率を所定の値以上に維持することができる。なお、加速度が大きくなる程、充電率が低下する。この結果、車両１０の航続距離が伸びた場合などに、車両１０を安定して走行させることができる。また、例えば、車両１０を日中（夜間）に一定の距離の範囲内で走行させつつ夜間（日中）に充電できるような場合に、酸化剤１４１及び還元剤１５１のエネルギーが消耗することを抑制できる。また、車両用フロー電池１００の電圧値を、一定の範囲内に制御して、駆動機器２５を安定して駆動させることができる。 According to such a control method (corresponding to the specific control method 1 described above), for example, when the vehicle 10 is traveled over a long distance, the charge rate of the vehicle flow battery 100 is set to a predetermined value or more. Can be maintained. The larger the acceleration, the lower the charge rate. As a result, when the cruising range of the vehicle 10 is extended, the vehicle 10 can be stably driven. Further, for example, when the vehicle 10 can be charged at night (daytime) while traveling within a certain distance during the daytime (nighttime), the energy of the oxidizing agent 141 and the reducing agent 151 is consumed. Can be suppressed. Further, the voltage value of the vehicle flow battery 100 can be controlled within a certain range to stably drive the drive device 25.

第１実施形態によれば、制御部１６０は、充電センサ１６１ｂにより測定される正極側の充電率が単位時間当たりに所定の割合を超えて減少した場合に、第１流通状態調整部（酸化部導入弁１４４及び酸化部導出弁１４６）により正極電解液１２２を正極側充電タンク１４２へ流通させるように制御する。制御部１６０による負極側の制御は、上記の正極側の制御と同様である。 According to the first embodiment, the control unit 160 is the first distribution state adjusting unit (oxidizing unit) when the charging rate on the positive electrode side measured by the charging sensor 161b decreases by more than a predetermined ratio per unit time. The introduction valve 144 and the oxide part lead-out valve 146) are used to control the positive electrode electrolyte 122 so as to flow to the positive electrode side charging tank 142. The control on the negative electrode side by the control unit 160 is the same as the control on the positive electrode side described above.

このような制御方法（上記した具体的な制御方法２に相当）によれば、例えば、車両１０が勾配の大きい坂道を走行するような場合に、車両用フロー電池１００の充電率が急速に減少することを抑制できる。この結果、車両１０に高負荷が発生しても、車両１０を安定して走行させることができる。また、例えば、車両１０が平地のような負荷が低い環境で走行するような場合に、酸化剤１４１及び還元剤１５１のエネルギーが消耗することを抑制できる。また、車両用フロー電池１００の電圧値を、一定の範囲内に制御して、駆動機器２５を安定して駆動させることができる。 According to such a control method (corresponding to the specific control method 2 described above), for example, when the vehicle 10 travels on a slope with a large slope, the charge rate of the vehicle flow battery 100 rapidly decreases. Can be suppressed. As a result, even if a high load is generated on the vehicle 10, the vehicle 10 can be stably driven. Further, for example, when the vehicle 10 travels in an environment with a low load such as a flat ground, it is possible to suppress the consumption of energy of the oxidizing agent 141 and the reducing agent 151. Further, the voltage value of the vehicle flow battery 100 can be controlled within a certain range to stably drive the drive device 25.

第１実施形態によれば、制御部１６０は、充電センサ１６１ｂにより測定される正極側の充電率が所定の値以上になるまで、第１流通状態調整部（酸化部導入弁１４４及び酸化部導出弁１４６）により正極側充電タンク１４２への正極電解液１２２の流量を調整する。制御部１６０による負極側の制御は、上記の正極側の制御と同様である。 According to the first embodiment, the control unit 160 is the first distribution state adjusting unit (oxidation unit introduction valve 144 and oxidation unit derivation) until the charge rate on the positive electrode side measured by the charge sensor 161b becomes a predetermined value or more. The flow rate of the positive electrode electrolyte 122 to the positive electrode side charging tank 142 is adjusted by the valve 146). The control on the negative electrode side by the control unit 160 is the same as the control on the positive electrode side described above.

このような制御方法（上記した具体的な制御方法３に相当）によれば、車両用フロー電池１００の電圧値を、一定の範囲内に制御することができる。この結果、車両用フロー電池１００から電力の供給を受ける駆動機器２５を、安定して駆動させることができる。また、車両１０の今後の走行状態を予測することが難しい場合でも、車両１０を安定して走行させることができる。 According to such a control method (corresponding to the specific control method 3 described above), the voltage value of the vehicle flow battery 100 can be controlled within a certain range. As a result, the drive device 25 that receives electric power from the vehicle flow battery 100 can be stably driven. Further, even when it is difficult to predict the future traveling state of the vehicle 10, the vehicle 10 can be stably traveled.

第１実施形態によれば、制御部１６０は、第１流通状態調整部（酸化部導入弁１４４及び酸化部導出弁１４６）により正極側充電タンク１４２に流通させる正極電解液１２２の流量を、正極セル１１２に循環させる正極電解液１２２の流量に対して増加させる。換言すると、酸化剤１４１に流通させる正極電解液１２２の流量Ｊ２を、正極セル１１２に循環させる正極電解液１２２の流量Ｊ１に対して増加させることによって、正極側の充電率を上昇させるように制御する。制御部１６０による負極側の制御は、上記の正極側の制御と同様である。 According to the first embodiment, the control unit 160 sets the flow rate of the positive electrode electrolyte 122 to be distributed to the positive electrode side charging tank 142 by the first flow state adjusting unit (oxidizing unit introduction valve 144 and oxidizing unit lead-out valve 146). It is increased with respect to the flow rate of the positive electrode electrolyte 122 circulated in the cell 112. In other words, the charge rate on the positive electrode side is increased by increasing the flow rate J2 of the positive electrode electrolyte 122 circulating in the oxidizing agent 141 with respect to the flow rate J1 of the positive electrode electrolyte 122 circulating in the positive electrode cell 112. To control. The control on the negative electrode side by the control unit 160 is the same as the control on the positive electrode side described above.

このような制御方法（上記した基本的な制御方法に相当）によれば、一定の応答性及び精度を満たした上で、車両用フロー電池１００の充電率を容易に制御することができる。この結果、車両用フロー電池１００から車両１０に対して安定的に電力を供給することができる。 According to such a control method (corresponding to the above-mentioned basic control method), the charge rate of the vehicle flow battery 100 can be easily controlled while satisfying certain responsiveness and accuracy. As a result, electric power can be stably supplied from the vehicle flow battery 100 to the vehicle 10.

「第２実施形態」
第２実施形態では、負極側充電タンク２５２が、正極側充電タンク１４２よりも小さく構成されている。 "Second embodiment"
In the second embodiment, the negative electrode side charging tank 252 is configured to be smaller than the positive electrode side charging tank 142.

第２実施形態の車両用フロー電池２００は、上記の構成のみが、第１実施形態の車両用フロー電池１００と異なる。第２実施形態では、第１実施形態と異なる構成について説明する。第２実施形態では、第１実施形態と同一の構成について、第１実施形態と同一の参照符号を付すことで、その説明を省略する。 The vehicle flow battery 200 of the second embodiment differs from the vehicle flow battery 100 of the first embodiment only in the above configuration. In the second embodiment, a configuration different from that of the first embodiment will be described. In the second embodiment, the same components as those in the first embodiment are designated by the same reference numerals as those in the first embodiment, and the description thereof will be omitted.

「車両用フロー電池２００に特有の構成」
図３を参照して、車両用フロー電池２００に特有の構成（還元部２５０）を説明する。なお、還元部２５０に関連して、酸化部１４０の酸化剤１４１についても説明する。 "Structure peculiar to the flow battery 200 for vehicles"
With reference to FIG. 3, a configuration (reducing unit 250) peculiar to the vehicle flow battery 200 will be described. The oxidizing agent 141 of the oxidizing unit 140 will also be described in relation to the reducing unit 250.

還元部２５０の還元剤１５１及び酸化部１４０の酸化剤１４１は、材料によって、それぞれ体積容量密度［Ａｈ／Ｌ］が異なる。体積容量密度［Ａｈ／Ｌ］は、単位体積［Ｌ］当たりに貯めることができる電流量［Ａｈ］である。還元剤１５１の体積容量密度［Ａｈ／Ｌ］は、Ｌｉ７Ｔｉ５Ｏ１２＜Ｌｉ金属＜Ｌｉ－Ｓｉ合金である。酸化剤１４１の体積容量密度［Ａｈ／Ｌ］は、ＦｅＰＯ４＜Ｎｉ０．５Ｍｎ１．５Ｏ４＜Ｍｎ２Ｏ４である。さらに、材料の組み合わせに依存するが、材料の物性上、還元剤１５１の体積容量密度［Ａｈ／Ｌ］は、酸化剤１４１の体積容量密度［Ａｈ／Ｌ］と比較して大きくなる場合が多い。 The volume volume density [Ah / L] of the reducing agent 151 of the reducing unit 250 and the oxidizing agent 141 of the oxidizing unit 140 differs depending on the material. The volume capacity density [Ah / L] is the amount of current [Ah] that can be stored per unit volume [L]. The volume volume density [Ah / L] of the reducing agent 151 is Li 7 Ti 5 O 12 <Li metal <Li—Si alloy. The volume volume density [Ah / L] of the oxidant 141 is FePO 4 <Ni 0.5 Mn 1.5 O 4 <Mn 2 O 4 . Further, although it depends on the combination of materials, the volume volume density [Ah / L] of the reducing agent 151 is often larger than the volume volume density [Ah / L] of the oxidizing agent 141 due to the physical characteristics of the materials. ..

すなわち、材料の組み合わせに依存するが、材料の物性上、負極側充電タンク２５２を正極側充電タンク１４２よりも小さく構成しても、負極側充電タンク２５２に充填される還元剤１５１の体積容量［Ａｈ］と、正極側充電タンク１４２に充填される酸化剤１４１の体積容量［Ａｈ］とを同等にすることができる。このようなことから、正極側充電タンク１４２の体積［Ｌ］と負極側充電タンク２５２の体積［Ｌ］との比が、酸化剤１４１の体積容量密度と還元剤１５１の体積容量密度との比の逆数と同等になるように、負極側充電タンク１５２の体積［Ｌ］を小さく設定する。 That is, although it depends on the combination of materials, even if the negative electrode side charging tank 252 is configured to be smaller than the positive electrode side charging tank 142 due to the physical characteristics of the materials, the volume capacity of the reducing agent 151 filled in the negative electrode side charging tank 252 [ Ah] can be made equivalent to the volume capacity [Ah] of the oxidizing agent 141 filled in the positive electrode side charging tank 142. Therefore, the ratio of the volume [L] of the positive charge tank 142 to the volume [L] of the negative charge tank 252 is the ratio of the volume volume density of the oxidizing agent 141 to the volume volume density of the reducing agent 151. The volume [L] of the negative charge side charging tank 152 is set small so as to be equivalent to the inverse number of.

具体的には、例えば、還元剤１５１の体積容量密度［Ａｈ／Ｌ］が酸化剤１４１の体積容量密度［Ａｈ／Ｌ］よりも５倍大きい場合、負極側充電タンク２５２の体積［Ｌ］が正極側充電タンク１４２の体積［Ｌ］の１／５になるように、負極側充電タンク２５２の体積［Ｌ］を小さく構成する。 Specifically, for example, when the volume volume density [Ah / L] of the reducing agent 151 is 5 times larger than the volume volume density [Ah / L] of the oxidizing agent 141, the volume [L] of the negative electrode side charging tank 252 becomes. The volume [L] of the negative side charging tank 252 is made small so as to be 1/5 of the volume [L] of the positive side charging tank 142.

「車両用フロー電池２００に特有の効果」
車両用フロー電池２００に特有の効果を説明する。 "Effects peculiar to vehicle flow battery 200"
The effect peculiar to the vehicle flow battery 200 will be described.

第２実施形態によれば、正極側充電タンク１４２の体積と負極側充電タンク２５２の体積との比が、酸化剤１４１の体積容量密度と還元剤１５１の体積容量密度との比の逆数に基づいて設定されている。 According to the second embodiment, the ratio of the volume of the positive electrode side charging tank 142 to the volume of the negative electrode side charging tank 252 is based on the inverse of the ratio of the volume volume density of the oxidizing agent 141 to the volume volume density of the reducing agent 151. Is set.

このような構成によれば、負極側充電タンク２５２を小型化することができる。この結果、車両用フロー電池２００を車両１０に設け易くすることができる。なお、車両用フロー電池２００を使用する場合に、正極側における酸化エネルギーと負極側における還元エネルギーとが同等になるように構成していることから、正極側又は負極側のどちらか一方のエネルギーが先に尽きて片方の充電タンク内の酸化剤（もしくは還元剤）のみ交換する状況を避けることができる。 According to such a configuration, the negative electrode side charging tank 252 can be miniaturized. As a result, the vehicle flow battery 200 can be easily provided in the vehicle 10. When the flow battery 200 for a vehicle is used, since the oxidation energy on the positive electrode side and the reduction energy on the negative electrode side are configured to be equal to each other, the energy of either the positive electrode side or the negative electrode side is equal. It is possible to avoid the situation where only the oxidizing agent (or reducing agent) in one of the charging tanks is replaced first.

さらに、このような構成によれば、例えば負極側充電タンク２５２を軽量化して、車両用フロー電池２００の重量を削減することができる。この結果、車両１０の航続距離を伸ばすことができる。また、車両１０に積載可能な荷物の重量を増加させることができる。 Further, according to such a configuration, for example, the weight of the negative electrode side charging tank 252 can be reduced, and the weight of the vehicle flow battery 200 can be reduced. As a result, the cruising range of the vehicle 10 can be extended. In addition, the weight of luggage that can be loaded on the vehicle 10 can be increased.

さらに、このような構成によれば、車両１０における正極側充電タンク１４２と負極側充電タンク１５２の設置スペースの上限が決まっている場合、正極側充電タンク１４２を負極側充電タンク１５２よりも相対的に大きく構成して、その設置スペースを上限まで無駄なく用いることができる。すなわち、負極側充電タンク１５２を相対的に小さくしつつ、負極側充電タンク１５２を小さくすることによって空いた設置スペースを、相対的に大きくした正極側充電タンク１４２のために用いることができる。この結果、車両１０の航続距離を最大化することができる。 Further, according to such a configuration, when the upper limit of the installation space of the positive electrode side charging tank 142 and the negative electrode side charging tank 152 in the vehicle 10 is determined, the positive electrode side charging tank 142 is relative to the negative electrode side charging tank 152. It can be configured to be large and the installation space can be used up to the upper limit without waste. That is, the installation space vacated by making the negative electrode side charging tank 152 relatively small while making the negative electrode side charging tank 152 relatively small can be used for the positive electrode side charging tank 142 which has been made relatively large. As a result, the cruising range of the vehicle 10 can be maximized.

さらに、このような構成によれば、例えば負極側充電タンク２５２の小型化に伴い、車両用フロー電池２００の製造コストを削減することができる。 Further, according to such a configuration, it is possible to reduce the manufacturing cost of the flow battery 200 for a vehicle, for example, with the miniaturization of the negative electrode side charging tank 252.

「第３実施形態」
第３実施形態では、正極側において、正極活物質１２１を含む正極電解液１２２が、正極セル１１２から導出された後に直接的に酸化部３４０に流通するように構成されている。負極側は、正極側と同様の構成としている。 "Third embodiment"
In the third embodiment, on the positive electrode side, the positive electrode electrolytic solution 122 containing the positive electrode active material 121 is configured to be directly distributed to the oxide unit 340 after being derived from the positive electrode cell 112. The negative electrode side has the same configuration as the positive electrode side.

第３実施形態の車両用フロー電池３００は、上記の構成のみが、第１及び第２実施形態の車両用フロー電池１００及び２００と異なる。第３実施形態では、第１及び第２実施形態と異なる構成について説明する。第３実施形態では、第１及び第２実施形態と同一の構成について、第１及び第２実施形態と同一の参照符号を付すことで、その説明を省略する。 The vehicle flow battery 300 of the third embodiment differs from the vehicle flow batteries 100 and 200 of the first and second embodiments only in the above configuration. In the third embodiment, a configuration different from the first and second embodiments will be described. In the third embodiment, the same components as those in the first and second embodiments are designated by the same reference numerals as those in the first and second embodiments, and the description thereof will be omitted.

「車両用フロー電池３００に特有の構成」
図４を参照して、車両用フロー電池３００に特有の構成（酸化部３４０及び還元部３５０）を説明する。 "Structure peculiar to the flow battery 300 for vehicles"
With reference to FIG. 4, a configuration (oxidation unit 340 and reduction unit 350) peculiar to the vehicle flow battery 300 will be described.

酸化部３４０において、正極側充電タンク１４２は、上流側は正極セル１１２に接続され、下流側は正極側溶液タンク１２３に接続されている。具体的には、酸化部３４０において、導出管３４５は、発電セル１１０の正極セル１１２と正極側充電タンク１４２との間に接続され、正極側酸化用ポンプ１４７が連結されている。導出管３４５には、導入弁３４６が設けられている。酸化部３４０では、酸化部導入弁１４４及び導入弁３４６が開かれた状態において、正極セル１１２から導出された正極電解液１２２が、正極側酸化用ポンプ１４７によって正極側充電タンク１４２に送液される。正極電解液１２２に含まれた正極活物質１２１は、発電セル１１０で還元された状態であり、正極側充電タンク１４２に収容された酸化剤１４１によって酸化される。酸化された正極活物質１２１を含む正極電解液１２２は、正極側溶液タンク１２３を介して正極セル１１２に送液される。 In the oxidizing portion 340, the positive electrode side charging tank 142 is connected to the positive electrode cell 112 on the upstream side and connected to the positive electrode side solution tank 123 on the downstream side. Specifically, in the oxidation unit 340, the lead-out pipe 345 is connected between the positive electrode cell 112 of the power generation cell 110 and the positive electrode side charging tank 142, and the positive electrode side oxidation pump 147 is connected. The lead-out pipe 345 is provided with an introduction valve 346. In the oxidizing section 340, the positive electrode electrolytic solution 122 derived from the positive electrode cell 112 is sent to the positive electrode side charging tank 142 by the positive electrode side oxidizing pump 147 in a state where the oxidizing section introduction valve 144 and the introduction valve 346 are opened. To. The positive electrode active material 121 contained in the positive electrode electrolytic solution 122 is in a reduced state in the power generation cell 110, and is oxidized by the oxidizing agent 141 contained in the positive electrode side charging tank 142. The positive electrode electrolytic solution 122 containing the oxidized positive electrode active material 121 is sent to the positive electrode cell 112 via the positive electrode side solution tank 123.

還元部３５０において、負極側充電タンク１５２は、上流側は負極セル１１４に接続され、下流側は負極側溶液タンク１３３に接続されている。具体的には、導出管３５５は、発電セル１１０の負極セル１１４と負極側充電タンク１５２との間に接続され、負極側還元用ポンプ１５７が連結されている。導出管３５５には、導入弁３５６が設けられている。還元部３５０では、還元部導入弁１５４及び導入弁３５６が開かれた状態において、負極セル１１４から導出された負極電解液１３２が、負極側還元用ポンプ１５７によって負極側充電タンク１５２に送液される。負極電解液１３２に含まれた負極活物質１３１は、発電セル１１０で酸化された状態であり、負極側充電タンク１５２に収容された還元剤１５１によって還元される。還元された負極活物質１３１を含む負極電解液１３２は、負極側溶液タンク１３３を介して負極セル１１４に送液される。 In the reduction unit 350, the negative electrode side charging tank 152 is connected to the negative electrode cell 114 on the upstream side and to the negative electrode side solution tank 133 on the downstream side. Specifically, the lead-out pipe 355 is connected between the negative electrode cell 114 of the power generation cell 110 and the negative electrode side charging tank 152, and the negative electrode side reduction pump 157 is connected. The lead-out pipe 355 is provided with an introduction valve 356. In the reduction section 350, the negative electrode electrolytic solution 132 led out from the negative electrode cell 114 is sent to the negative electrode side charging tank 152 by the negative electrode side reduction pump 157 in a state where the reduction section introduction valve 154 and the introduction valve 356 are opened. To. The negative electrode active material 131 contained in the negative electrode electrolyte 132 is in a state of being oxidized in the power generation cell 110, and is reduced by the reducing agent 151 contained in the negative electrode side charging tank 152. The negative electrode electrolytic solution 132 containing the reduced negative electrode active material 131 is sent to the negative electrode cell 114 via the negative electrode side solution tank 133.

「車両用フロー電池３００に特有の効果」
車両用フロー電池３００に特有の効果を説明する。 "Effects peculiar to vehicle flow battery 300"
The effect peculiar to the vehicle flow battery 300 will be described.

第３実施形態によれば、正極側充電タンク１４２は、上流側は正極セル１１２に接続され、下流側は正極側溶液タンク１２３に接続されている。同様に、負極側充電タンク１５２は、上流側は負極セル１１４に接続され、下流側は負極側溶液タンク１３３に接続されている。 According to the third embodiment, the positive electrode side charging tank 142 is connected to the positive electrode cell 112 on the upstream side and connected to the positive electrode side solution tank 123 on the downstream side. Similarly, the negative electrode side charging tank 152 is connected to the negative electrode cell 114 on the upstream side and to the negative electrode side solution tank 133 on the downstream side.

このような構成によれば、正極セル１１２に循環されて還元された（エネルギーを消耗した）正極活物質１２１を、エネルギーの供給源である酸化剤１４１に直送して、速やかに酸化させる（エネルギーを与える）ことができる。また、負極セル１１４に循環されて酸化された（エネルギーを消耗した）負極活物質１３１を、エネルギーの供給源である還元剤１５１に直送して、速やかに還元させる（エネルギーを与える）ことができる。すなわち、エネルギーを消耗した正極活物質１２１及び負極活物質１３１に対して、それぞれ効率良くエネルギーを供給することができる。この結果、車両１０を安定して航続させることができる。 According to such a configuration, the positive electrode active material 121 that has been circulated and reduced (energy consumed) in the positive electrode cell 112 is directly sent to the oxidizing agent 141 that is an energy supply source to be rapidly oxidized (energy). Can be given). Further, the negative electrode active material 131 circulated in the negative electrode cell 114 and oxidized (energy consumed) can be directly sent to the reducing agent 151 which is an energy supply source to be rapidly reduced (energy is given). .. That is, energy can be efficiently supplied to the positive electrode active material 121 and the negative electrode active material 131 that have consumed energy. As a result, the vehicle 10 can be stably navigated.

特に、このような構成によれば、例えば車両１０を長距離にわたり走行させるような場合に、エネルギーを消耗した正極活物質１２１及び負極活物質１３１に対して、それぞれ直接的にエネルギーを供給し続けることができる。この結果、長距離走行時においても、車両１０を安定して航続させることができる。 In particular, according to such a configuration, for example, when the vehicle 10 is traveled over a long distance, the energy is continuously supplied directly to the energy-consumed positive electrode active material 121 and the negative electrode active material 131, respectively. be able to. As a result, the vehicle 10 can be stably maintained even during long-distance traveling.

「第１～第３実施形態の変形例」
なお、本発明を実施するに当たり、上記した第１～第３実施形態の構成は、一例であり、種々変更して実施することができる。 "Modified examples of the first to third embodiments"
In carrying out the present invention, the configurations of the first to third embodiments described above are examples, and can be variously modified and carried out.

上記した第１～第３実施形態においては、活物質の組み合わせとして、鉄－コバルトを想定している。これに代えて、活物質の組み合わせとして、例えば、ヨウ素－コバルト、又は鉄－クロムとしてもよい。 In the first to third embodiments described above, iron-cobalt is assumed as the combination of active substances. Alternatively, the combination of active substances may be, for example, iodine-cobalt or iron-chromium.

上記した第１～第３実施形態においては、車両１０は、車両用フロー電池１００、２００及び３００を電源として車載用モータを駆動する電気自動車を想定しているが、ガソリンを燃料とするエンジンを併用する構成としてもよい。 In the first to third embodiments described above, the vehicle 10 is assumed to be an electric vehicle that uses vehicle flow batteries 100, 200, and 300 as a power source to drive an in-vehicle motor, but uses a gasoline-fueled engine. It may be configured to be used together.

上記した第２実施形態においては、還元剤１５１の体積容量密度と酸化剤１４１の体積容量密度との比に応じて、例えば、負極側充電タンク２５２の体積を正極側充電タンク１４２の体積よりも小さくする構成を想定している。これに代えて、還元剤１５１の体積容量密度と酸化剤１４１の体積容量密度とが同等であって、かつ、負極側充電タンク１５２の体積と正極側充電タンク１４２の体積とが同等になるように、還元剤１５１の材料と酸化剤１４１の材料とを選定する構成としてもよい。 In the second embodiment described above, for example, the volume of the negative electrode side charging tank 252 is larger than the volume of the positive electrode side charging tank 142 according to the ratio of the volume volume density of the reducing agent 151 to the volume volume density of the oxidizing agent 141. It is supposed to be made smaller. Instead, the volume volume density of the reducing agent 151 and the volume volume density of the oxidizing agent 141 are equal to each other, and the volume of the negative charge tank 152 and the volume of the positive charge tank 142 are equal. In addition, the material of the reducing agent 151 and the material of the oxidizing agent 141 may be selected.

１０…車両、２０…電気ユニット、２１…給電部、２２…インバータ、２３…正極端子、２４…負極端子、２５…駆動機器、１００…車両用フロー電池、１１０…発電セル、１１１…正極電極、１１２…正極セル、１１３…負極電極、１１４…負極セル、１１５…隔膜、１２０…正極側循環部、１２１…正極活物質、１２１ａ…２価の正極活物質、１２１ｂ…３価の正極活物質、１２２…正極電解液、１２３…正極側溶液タンク、１２４…正極側循環部導入管（正極側循環配管）、１２５…正極側循環部導出管（正極側循環配管）、１２６…正極側循環用ポンプ、１３０…負極側循環部、１３１…負極活物質、１３１ａ…３価の負極活物質、１３１ｂ…２価の負極活物質、１３２…負極電解液、１３３…負極側溶液タンク、１３４…負極側循環部導入管（負極側循環配管）、１３５…負極側循環部導出管（負極側循環配管）、１３６…負極側循環用ポンプ、１４０…酸化部、１４１…酸化剤（酸化部材）、１４２…正極側充電タンク（酸化部材収容部）、１４３…酸化部導入管、１４４…酸化部導入弁（第１流通状態調整部の正極側開閉弁）、１４５…酸化部導出管、１４６…酸化部導出弁（第１流通状態調整部の正極側開閉弁）、１４７…正極側酸化用ポンプ、１５０…還元部、１５１…還元剤（還元部材）、１５２…負極側充電タンク、１５３…還元部導入管、１５４…還元部導入弁（第２流通状態調整部の負極側開閉弁）、１５５…還元部導出管、１５６…還元部導出弁（第２流通状態調整部の負極側開閉弁）、１５７…負極側還元用ポンプ、１６０…制御部、１６１ａ…加速センサ、１６１ｂ…充電センサ、２００…車両用フロー電池、２５０…還元部、２５２…負極側充電タンク、３００…車両用フロー電池、３２０…正極側循環部、３３０…負極側循環部、３４０…酸化部、３４５…導出管、３４６…導入弁、３５０…還元部、３５５…導出管、３５６…導入弁。 10 ... vehicle, 20 ... electric unit, 21 ... power supply unit, 22 ... inverter, 23 ... positive electrode terminal, 24 ... negative electrode terminal, 25 ... drive equipment, 100 ... vehicle flow battery, 110 ... power generation cell, 111 ... positive electrode electrode, 112 ... positive electrode cell, 113 ... negative electrode, 114 ... negative electrode cell, 115 ... diaphragm, 120 ... positive electrode side circulation part, 121 ... positive electrode active material, 121a ... divalent positive electrode active material, 121b ... trivalent positive electrode active material, 122 ... Positive electrode electrolyte, 123 ... Positive electrode side solution tank, 124 ... Positive electrode side circulation section introduction pipe (positive electrode side circulation pipe), 125 ... Positive electrode side circulation section lead-out pipe (positive electrode side circulation pipe), 126 ... Positive electrode side circulation pump , 130 ... Negative electrode side circulation part, 131 ... Negative electrode active material, 131a ... Trivalent negative electrode active material, 131b ... Divalent negative electrode active material, 132 ... Negative electrode electrolyte, 133 ... Negative electrode side solution tank, 134 ... Negative electrode side circulation Part introduction pipe (negative electrode side circulation pipe), 135 ... negative electrode side circulation part lead-out pipe (negative electrode side circulation pipe) 136 ... negative electrode side circulation pump, 140 ... oxide part, 141 ... oxidant (oxidizing member), 142 ... positive electrode Side charging tank (oxidizing member accommodating part), 143 ... oxide part introduction tube, 144 ... oxide part introduction valve (positive electrode side on-off valve of the first flow state adjusting part), 145 ... oxide part lead-out tube, 146 ... oxide part lead-out valve (Positive side on-off valve of the first distribution state adjusting part) 147 ... Positive electrode side oxidation pump, 150 ... Reducing part, 151 ... Reducing agent (reducing member), 152 ... Negative electrode side charging tank, 153 ... Reducing part introduction tube, 154 ... Reduction section introduction valve (negative electrode side on-off valve of the second flow state adjustment section), 155 ... Reduction section lead-out tube, 156 ... Reduction section lead-out valve (negative electrode side on-off valve of the second flow state adjustment section), 157 ... Negative electrode Side reduction pump, 160 ... control unit, 161a ... acceleration sensor, 161b ... charge sensor, 200 ... vehicle flow battery, 250 ... reduction unit, 252 ... negative electrode side charging tank, 300 ... vehicle flow battery, 320 ... positive electrode side Circulation section, 330 ... Negative electrode side circulation section, 340 ... Oxidation section, 345 ... Outlet tube, 346 ... Introduction valve, 350 ... Reduction section, 355 ... Outlet tube, 356 ... Introduction valve.

Claims (10)

正極電極が収容された正極セルと、負極電極が収容された負極セルと、を有する発電セルと、
正極活物質を含む正極電解液を貯蔵する正極側溶液タンクを有し、正極側循環配管を介して前記正極セルと該正極側溶液タンクとの間で該正極電解液を循環させる正極側循環部と、
負極活物質を含む負極電解液を貯蔵する負極側溶液タンクを有し、負極側循環配管を介して前記負極セルと該正極側溶液タンクとの間で該負極電解液を循環させる負極側循環部と、を備えた車両用フロー電池であって、
酸化部材を収容する酸化部材収容部を有し、前記正極電解液を該酸化部材収容部へ流通させる酸化部と、
還元部材を収容する還元部材収容部を有し、前記負極電解液を該還元部材収容部へ流通させる還元部と、
前記正極電解液の前記酸化部材収容部への流通状態を調整する第１流通状態調整部と、
前記負極電解液の前記還元部材収容部への流通状態を調整する第２流通状態調整部と、
前記第１流通状態調整部及び前記第２流通状態調整部を制御する制御部と、を有する車両用フロー電池。 A power generation cell having a positive electrode cell containing a positive electrode and a negative electrode cell containing a negative electrode.
A positive electrode side circulation unit which has a positive electrode side solution tank for storing a positive electrode electrolytic solution containing a positive electrode active material and circulates the positive electrode side electrolytic solution between the positive electrode cell and the positive electrode side solution tank via a positive electrode side circulation pipe. When,
A negative electrode side circulation unit which has a negative electrode side solution tank for storing a negative electrode electrolytic solution containing a negative electrode active material and circulates the negative electrode side electrolytic solution between the negative electrode cell and the positive electrode side solution tank via a negative electrode side circulation pipe. It is a flow battery for vehicles equipped with
An oxidizing unit having an oxidizing member accommodating portion for accommodating the oxidizing member and distributing the positive electrode electrolytic solution to the oxidizing member accommodating portion.
A reducing unit having a reducing member accommodating portion for accommodating the reducing member and distributing the negative electrode electrolytic solution to the reducing member accommodating portion.
A first flow state adjusting unit for adjusting the flow state of the positive electrode electrolyte solution to the oxidizing member accommodating part, and a first flow state adjusting unit.
A second distribution state adjusting unit for adjusting the distribution state of the negative electrode electrolytic solution to the reducing member accommodating unit, and a second distribution state adjusting unit.
A flow battery for a vehicle having a first distribution state adjusting unit and a control unit that controls the second distribution state adjusting unit. 前記酸化部材収容部は、前記正極側溶液タンクに対して並列に接続され、
前記還元部材収容部は、前記負極側溶液タンクに対して並列に接続され、
前記第１流通状態調整部は、前記酸化部材収容部の上流側及び下流側の少なくとも一方に設けられた正極側開閉弁を含み、
前記第２流通状態調整部は、前記還元部材収容部の上流側及び下流側の少なくとも一方に設けられた負極側開閉弁を含む、請求項１に記載の車両用フロー電池。 The oxidizing member accommodating portion is connected in parallel to the positive electrode side solution tank, and is connected in parallel.
The reducing member accommodating portion is connected in parallel to the negative electrode side solution tank, and is connected to the negative electrode side solution tank.
The first distribution state adjusting unit includes a positive electrode side on-off valve provided on at least one of the upstream side and the downstream side of the oxidizing member accommodating unit.
The flow battery for a vehicle according to claim 1, wherein the second distribution state adjusting unit includes a negative electrode side on-off valve provided on at least one of an upstream side and a downstream side of the reducing member accommodating unit. 前記酸化部材収容部は、上流側は前記正極セルに接続され、下流側は前記正極側溶液タンクに接続され、
前記還元部材収容部は、上流側は前記負極セルに接続され、下流側は前記負極側溶液タンクに接続され、
前記第１流通状態調整部は、前記正極セルと前記酸化部材収容部との間及び前記酸化部材収容部と前記正極側溶液タンクとの間の少なくとも一方に設けられた正極側開閉弁を含み、
前記第２流通状態調整部は、前記負極セルと前記還元部材収容部との間及び前記還元部材収容部と前記負極側溶液タンクとの間の少なくとも一方に設けられた負極側開閉弁を含む、請求項１に記載の車両用フロー電池。 The oxidizing member accommodating portion is connected to the positive electrode cell on the upstream side and connected to the positive electrode side solution tank on the downstream side.
The reducing member accommodating portion is connected to the negative electrode cell on the upstream side and connected to the negative electrode side solution tank on the downstream side.
The first distribution state adjusting unit includes a positive electrode side on-off valve provided between the positive electrode cell and the oxidizing member accommodating portion and at least one of the oxidizing member accommodating portion and the positive electrode side solution tank.
The second distribution state adjusting unit includes a negative electrode side on-off valve provided between the negative electrode cell and the reducing member accommodating portion and at least one of the reducing member accommodating portion and the negative electrode side solution tank. The vehicle flow battery according to claim 1. 前記酸化部材収容部の体積と前記還元部材収容部の体積との比が、前記酸化部材の体積容量密度と前記還元部材の体積容量密度との比の逆数に基づいて設定された、請求項１～３の何れか一項に記載の車両用フロー電池。 Claim 1 in which the ratio of the volume of the oxidizing member accommodating portion to the volume of the reducing member accommodating portion is set based on the inverse of the ratio of the volume volume density of the oxidizing member and the volume volume density of the reducing member. The vehicle flow battery according to any one of 3 to 3. 前記酸化部材収容部及び前記還元部材収容部の少なくとも一方が、車両に対して少なくとも交換可能又は補充可能に構成された、請求項１～４の何れか一項に記載の車両用フロー電池。 The flow battery for a vehicle according to any one of claims 1 to 4, wherein at least one of the oxidizing member accommodating portion and the reducing member accommodating portion is configured to be at least replaceable or replenishable with respect to the vehicle. 前記制御部は、車両の加速状態を測定する加速状態測定手段を更に有し、
前記制御部は、
前記加速状態測定手段により測定される加速度が所定値以上の場合に、前記第１流通状態調整部により前記正極電解液を前記酸化部材収容部へ流通させ、
前記第２流通状態調整部により前記負極電解液を前記還元部材収容部へ流通させる、請求項１～５の何れか一項に記載の車両用フロー電池。 The control unit further includes an acceleration state measuring means for measuring the acceleration state of the vehicle.
The control unit
When the acceleration measured by the acceleration state measuring means is equal to or higher than a predetermined value, the positive electrode electrolytic solution is circulated to the oxidizing member accommodating section by the first flow state adjusting section.
The flow battery for a vehicle according to any one of claims 1 to 5, wherein the negative electrode electrolytic solution is circulated to the reducing member accommodating portion by the second distribution state adjusting unit. 前記制御部は、正極側及び負極側の充電率を測定する充電率測定手段を更に有し、
前記制御部は、
前記充電率測定手段により測定される正極側の充電率が所定の値未満となった場合に、
前記第１流通状態調整部により前記正極電解液を前記酸化部材収容部へ流通させ、
前記充電率測定手段により測定される負極側の充電率が所定の値未満となった場合に、
前記第２流通状態調整部により前記負極電解液を前記還元部材収容部へ流通させる、請求項１～５の何れか一項に記載の車両用フロー電池。 The control unit further includes a charge rate measuring means for measuring the charge rates on the positive electrode side and the negative electrode side.
The control unit
When the charge rate on the positive electrode side measured by the charge rate measuring means is less than a predetermined value,
The positive electrode electrolytic solution is circulated to the oxidizing member accommodating portion by the first distribution state adjusting unit.
When the charge rate on the negative electrode side measured by the charge rate measuring means is less than a predetermined value,
The flow battery for a vehicle according to any one of claims 1 to 5, wherein the negative electrode electrolytic solution is circulated to the reducing member accommodating portion by the second distribution state adjusting unit. 前記制御部は、正極側及び負極側の充電率を測定する充電率測定手段を更に有し、
前記制御部は、
前記充電率測定手段により測定される正極側の充電率が単位時間当たりに所定の割合を超えて減少した場合に、前記第１流通状態調整部により前記正極電解液を前記酸化部材収容部へ流通させ、
前記充電率測定手段により測定される負極側の充電率が単位時間当たりに所定の割合を超えて減少した場合に、前記第２流通状態調整部により前記負極電解液を前記還元部材収容部へ流通させる、請求項１～５の何れか一項に記載の車両用フロー電池。 The control unit further includes a charge rate measuring means for measuring the charge rates on the positive electrode side and the negative electrode side.
The control unit
When the charge rate on the positive electrode side measured by the charge rate measuring means decreases by more than a predetermined ratio per unit time, the positive electrode electrolytic solution is distributed to the oxidizing member accommodating unit by the first flow state adjusting unit. Let me
When the charge rate on the negative electrode side measured by the charge rate measuring means decreases by more than a predetermined ratio per unit time, the negative electrode electrolytic solution is distributed to the reduction member accommodating unit by the second flow state adjusting unit. The flow battery for a vehicle according to any one of claims 1 to 5. 前記制御部は、
前記充電率測定手段により測定される正極側の充電率が所定の値以上になるまで、前記第１流通状態調整部により前記酸化部材収容部への前記正極電解液の流量を調整し、
前記充電率測定手段により測定される負極側の充電率が所定の値以上になるまで、前記第２流通状態調整部により前記還元部材収容部への前記負極電解液の流量を調整する、請求項７または８に記載の車両用フロー電池。 The control unit
The flow rate of the positive electrode electrolytic solution to the oxidizing member accommodating portion is adjusted by the first distribution state adjusting unit until the charging rate on the positive electrode side measured by the charging rate measuring means becomes a predetermined value or more.
The claim that the flow rate of the negative electrode electrolytic solution to the reducing member accommodating portion is adjusted by the second distribution state adjusting unit until the charging rate on the negative electrode side measured by the charging rate measuring means becomes a predetermined value or more. The vehicle flow battery according to 7 or 8. 前記制御部は、
前記第１流通状態調整部により前記酸化部材収容部に流通させる前記正極電解液の流量を、前記正極セルに循環させる前記正極電解液の流量に対して増加させ、
前記第１流通状態調整部により前記還元部材収容部に流通させる前記負極電解液の流量を、前記負極セルに循環させる前記負極電解液の流量に対して増加させる、請求項１～９の何れか一項に記載の車両用フロー電池。 The control unit
The flow rate of the positive electrode electrolytic solution to be distributed to the oxidizing member accommodating unit by the first distribution state adjusting unit is increased with respect to the flow rate of the positive electrode electrolytic solution to be circulated in the positive electrode cell.
Any of claims 1 to 9, wherein the flow rate of the negative electrode electrolytic solution circulated in the reducing member accommodating section by the first distribution state adjusting section is increased with respect to the flow rate of the negative electrode electrolytic solution circulated in the negative electrode cell. The vehicle flow battery according to item 1.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012226974A (en) 2011-04-20 2012-11-15 Honda Motor Co Ltd Redox fuel cell system and fuel cell vehicle
JP2017500692A (en) 2013-11-12 2017-01-05 アカル エネルギー リミテッド Fuel cell assembly and method for operating the fuel cell assembly by monitoring oxidation status
JP2018106913A (en) 2016-12-26 2018-07-05 トヨタ自動車株式会社 Fuel cell system

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012226974A (en) 2011-04-20 2012-11-15 Honda Motor Co Ltd Redox fuel cell system and fuel cell vehicle
JP2017500692A (en) 2013-11-12 2017-01-05 アカル エネルギー リミテッド Fuel cell assembly and method for operating the fuel cell assembly by monitoring oxidation status
JP2018106913A (en) 2016-12-26 2018-07-05 トヨタ自動車株式会社 Fuel cell system

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