JPH0758625B2 - Redox battery - Google Patents
Redox batteryInfo
- Publication number
- JPH0758625B2 JPH0758625B2 JP2121764A JP12176490A JPH0758625B2 JP H0758625 B2 JPH0758625 B2 JP H0758625B2 JP 2121764 A JP2121764 A JP 2121764A JP 12176490 A JP12176490 A JP 12176490A JP H0758625 B2 JPH0758625 B2 JP H0758625B2
- Authority
- JP
- Japan
- Prior art keywords
- active material
- redox
- positive electrode
- solution
- electrode side
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 35
- 239000011149 active material Substances 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 229910052720 vanadium Inorganic materials 0.000 claims description 16
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000002798 polar solvent Substances 0.000 claims description 12
- -1 halogen ion Chemical class 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 description 16
- 238000003411 electrode reaction Methods 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229940074995 bromine Drugs 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229960002358 iodine Drugs 0.000 description 3
- 150000002506 iron compounds Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 150000003682 vanadium compounds Chemical class 0.000 description 3
- 229910001456 vanadium ion Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000013626 chemical specie Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- FALYLKWQXGKTGO-UHFFFAOYSA-N Cl.[Cr].[Fe] Chemical compound Cl.[Cr].[Fe] FALYLKWQXGKTGO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- FYMBCBXJSPPHJQ-UHFFFAOYSA-N [Br].[V] Chemical compound [Br].[V] FYMBCBXJSPPHJQ-UHFFFAOYSA-N 0.000 description 1
- FCMKFNXOHUYWRU-UHFFFAOYSA-N [Cl].[Cr] Chemical compound [Cl].[Cr] FCMKFNXOHUYWRU-UHFFFAOYSA-N 0.000 description 1
- YJGYYHATLSELPD-UHFFFAOYSA-N [V].[Cl] Chemical compound [V].[Cl] YJGYYHATLSELPD-UHFFFAOYSA-N 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 229960003284 iron Drugs 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Fuel Cell (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） この発明は、レドックス電池に関し、更に詳しくはバナ
ジウム−ハロゲン、バナジウム−鉄をレドックス対とす
るレドックス・フロー型二次電池に関するものである。Description: TECHNICAL FIELD The present invention relates to a redox battery, and more particularly to a redox flow secondary battery having a vanadium-halogen or vanadium-iron as a redox pair.
（従来の技術） レドックス・フロー型二次電池は、液状の正、負極の電
池活物質を液透過型の電解槽に流通せしめ、酸化還元反
応を利用して充放電を行なうものである。従来の二次電
池と比較してレドックス・フロー型二次電池は次の利点
を有する。(Prior Art) A redox flow type secondary battery is one in which liquid positive and negative battery active materials are circulated in a liquid permeation type electrolytic cell, and charging and discharging are performed by utilizing an oxidation-reduction reaction. The redox flow type secondary battery has the following advantages as compared with the conventional secondary battery.
（１）蓄電容量を大きくするためには、蓄電容器の容量
を大きくし、活物質量を増加させるだけでよく、出力を
大きくしない限り、電解槽自体はそのままでよい。(1) In order to increase the storage capacity, it is only necessary to increase the capacity of the storage container and increase the amount of the active material, and the electrolytic cell itself may be used as long as the output is not increased.
（２）正、負極活物質を容器に完全に分離して貯蔵でき
るので、活物質が電極に接しているような電池と異な
り、自己放電の可能性が小さい。(2) Since positive and negative electrode active materials can be completely separated and stored in a container, unlike a battery in which the active material is in contact with the electrodes, the possibility of self-discharge is small.
（３）本電池で使用する液透過型炭素多孔質電極におい
ては、活物質イオンの充放電反応（電極反応）は、単に
電極表面で電子の交換を行なうのみで、亜鉛イオンのよ
うに電極に析出することはないので、電池の反応が単純
である。(3) In the liquid permeable carbon porous electrode used in the present battery, the charge / discharge reaction (electrode reaction) of the active material ions simply involves exchanging electrons on the electrode surface, and the same as the zinc ion to the electrode. The reaction of the battery is simple because it does not precipitate.
現在、実用化段階にあると見られているクロム２価、３
価対鉄２価、３価系をレドックス対とするレドックス・
フロー型二次電池は、使用目的によっては極めて性能の
優れた電池であるが、長期間の運転に対しては、電解槽
の隔膜を通しての鉄とクロムとの相互混合が避けられ
ず、結局、両活物質ともに鉄とクロムの混合液となり、
溶解度の制約を受けるため、濃厚溶液とすることができ
ないという欠点がある。Chromium divalent, 3 currently considered to be in practical use
Redox with a redox pair consisting of iron and iron
The flow type secondary battery is a battery having extremely excellent performance depending on the purpose of use, but for long-term operation, mutual mixing of iron and chromium through the diaphragm of the electrolytic cell is unavoidable, and in the end, Both active materials become a mixed solution of iron and chromium,
It has a drawback that it cannot be made into a concentrated solution because it is limited in solubility.
また、クロム、鉄系の電池の場合、出力電圧は単セル当
たり0.9〜1V程度であるので、この電池のエネルギー密
度（即ち放電によって取り出し得るエネルギーを電池の
体積で割った値）は30Wh/l程度にしかならない。Also, in the case of chromium and iron type batteries, the output voltage is about 0.9 to 1 V per cell, so the energy density of this battery (that is, the value obtained by dividing the energy that can be taken out by discharging by the volume of the battery) is 30Wh / l. It is nothing more than a degree.
以上の欠点を改善するレドックス・フロー型二次電池と
して、クロム、塩素系のレドックス対等を用いることが
提案され、改良されている（特開昭61−24172号）。It has been proposed and improved to use a chromium / chlorine redox couple or the like as a redox flow type secondary battery for improving the above-mentioned drawbacks (Japanese Patent Laid-Open No. 61-24172).
（発明が解決しようとする問題点） しかし、クロム、塩素系のレドックス対では、隔膜とし
て使用するイオン交換膜の電気抵抗を下げる目的で、陽
イオン交換膜を選択して、水素イオンを泳動させる方式
であるため、高濃度の塩酸が使用されている。ところ
が、クロム２価/3価イオンのレドックス電位は水素発生
電位に近く、しかもクロム系負極液での電極反応は遅
く、酸が高濃度になるほど、この水素ガス発生の副反応
が増大し、効率低下の原因になる。(Problems to be solved by the invention) However, in a chromium- and chlorine-based redox couple, a cation-exchange membrane is selected to migrate hydrogen ions in order to lower the electric resistance of the ion-exchange membrane used as a diaphragm. Since it is a system, high concentration hydrochloric acid is used. However, the redox potential of divalent / three valent chromium ions is close to the hydrogen generation potential, and the electrode reaction in the chrome-based negative electrode liquid is slow, and the higher the concentration of acid, the greater the side reaction of hydrogen gas generation, and the higher the efficiency. Cause a drop.
また、クロム、塩素系のレドックス対では、塩素を活物
質として使用するため、高濃度の塩化物イオンを必要と
するが、高濃度の塩化物イオンの共存によりクロムイオ
ンの溶解度が減少する。In addition, since chromium and chlorine-based redox couples use chlorine as an active material, a high concentration of chloride ions is required, but the coexistence of high concentration of chloride ions reduces the solubility of chromium ions.
更に、正、負極での電極反応を向上しうる活物質とし
て、鉄、銅、スズ、ニッケル、ハロゲンなどのハロゲン
酸性溶液を使用する提案もなされているが（特開昭60−
207258号）、何れの組合わせも単電池当たりの起電力が
小さかったり、電極へ金属が析出する複雑な電極反応で
あったり、一長一短がある。Further, it has been proposed to use a halogen acid solution of iron, copper, tin, nickel, halogen or the like as an active material capable of improving the electrode reaction in positive and negative electrodes (JP-A-60-
No. 207258), any combination has advantages and disadvantages such as a small electromotive force per cell and a complicated electrode reaction in which metal is deposited on the electrodes.
一方、硫酸溶液に溶解したバナジウムの４価/5価系と３
価/2価系のイオン対を正、負極液とした全バナジウムレ
ドックス・フロー型電池が提案されているが（特開昭62
−186473号）、これは大変高価なバナジウムを正、負極
液として使用するため、実用的な価値に乏しい。On the other hand, the vanadium tetravalent and pentavalent systems dissolved in sulfuric acid solution
An all-vanadium redox flow type battery has been proposed in which a valence / valence 2 ion pair is used as a positive and negative electrode solution (JP-A-62-62
No. 186473), which uses very expensive vanadium as the positive and negative electrode liquids, and is of little practical value.
そこで、この発明の目的は、負極での水素発生を伴わな
いレドックス系二次電池を供給することにある。Therefore, an object of the present invention is to supply a redox-based secondary battery that does not generate hydrogen at the negative electrode.
また、この発明の目的は電解液混合が問題とならないレ
ドックス対を用いて、電池の充放電効率を向上させ、充
放電サイクル回数を重ね得るレドックス二次電池を供給
することにある。Another object of the present invention is to provide a redox secondary battery which can improve the charge / discharge efficiency of the battery and increase the number of charge / discharge cycles by using a redox pair in which mixing of an electrolyte solution does not pose a problem.
（問題点を解決するための手段） この発明は、以上の問題点を解決するため、新しい組合
わせのレドックス対を極性溶媒に溶解した電解液を開発
し、短時間率高性能レドックス二次電池を供給するもの
である。(Means for Solving Problems) In order to solve the above problems, the present invention has developed an electrolytic solution in which a redox pair of a new combination is dissolved in a polar solvent, and has a short-term high-performance redox secondary battery. To supply.
具体的には、この発明のレドックス型二次電池はレドッ
クス対の負極側の活物質を極性溶媒中に溶解させたバナ
ジウム２価、３価の溶液で構成し、レドックス対の正極
側の活物質をハロゲン、ハロゲンイオンの溶液乃至極性
溶媒中に溶解させた鉄２価、３価の溶液で構成し、該レ
ドックス対を液透過型の電解槽に送液して充放電を行な
うものである。Specifically, the redox type secondary battery of the present invention is composed of a vanadium divalent and trivalent solution in which a negative active material of a redox pair is dissolved in a polar solvent. Is composed of a solution of halogen and a halogen ion or an iron divalent or trivalent solution dissolved in a polar solvent, and the redox couple is fed to a liquid permeation type electrolytic cell for charging and discharging.
ここで、２価、３価のバナジウム化合物としては硫酸バ
ナジウム等を使用することができる。Here, vanadium sulfate or the like can be used as the divalent or trivalent vanadium compound.
また、バナジウム化合物を溶解する極性溶媒としてはバ
ナジウムの溶解性が損なわれず、電極反応速度を良好に
するので、硫酸又は硫酸と塩酸の混合液が好ましいが、
塩酸、臭化水素酸、或は極性の有機溶媒等を使用するこ
ともできる。また、これらの溶媒を単独で使用すること
ができるが、その２種以上を混合して使用することもで
きる。Further, as the polar solvent for dissolving the vanadium compound, the solubility of vanadium is not impaired and the electrode reaction rate is improved, so sulfuric acid or a mixed solution of sulfuric acid and hydrochloric acid is preferable,
It is also possible to use hydrochloric acid, hydrobromic acid, or a polar organic solvent. Further, these solvents can be used alone, or two or more of them can be mixed and used.
負極側の活物質は、例えば硫酸バナジルを硫酸乃至硫酸
と塩酸或は硫酸と臭化水素酸の混合液に溶解し、電解還
元することによって容易に調整することができる。The active material on the negative electrode side can be easily prepared, for example, by dissolving vanadyl sulfate in sulfuric acid or a mixed solution of sulfuric acid and hydrochloric acid or a mixed solution of sulfuric acid and hydrobromic acid and electrolytically reducing it.
一方、正極側活物質のハロゲン、ハロゲンイオン溶液と
しては塩素、塩化物イオン、臭素、臭化物イオン、ヨウ
素、ヨウ化物イオンの少なくとも１種を0.1〜８モル/l
含有する溶液を使用することができる。On the other hand, as the halogen or halogen ion solution of the positive electrode side active material, at least one of chlorine, chloride ion, bromine, bromide ion, iodine and iodide ion is used in an amount of 0.1 to 8 mol / l.
The containing solution can be used.
この場合、１種類のハロゲン、ハロゲンイオン溶液で正
極側活物質を構成してもよいが、２種以上のハロゲン、
ハロゲンイオン溶液で正極側活物質を構成してもよい。
例えば、塩酸中に臭化水素酸を混合して正極側活物質を
構成してもよい。In this case, the positive electrode side active material may be composed of one kind of halogen or a halogen ion solution, but two or more kinds of halogen,
You may comprise a positive electrode side active material with a halogen ion solution.
For example, the positive electrode-side active material may be formed by mixing hydrobromic acid in hydrochloric acid.
また、２価、３価の鉄化合物としては塩化物、硫酸化合
物等を使用することができ、これらの鉄化合物を溶解さ
せる極性溶媒としては鉄の溶解性を損なわず、電極反応
速度を良好にするため、塩酸又は塩酸と硫酸の混合液が
好ましいが、臭化水素酸或は極性の有機溶媒等を使用す
ることができる。この場合、正極側の活物質の調整に際
しては例えば塩酸中に２価、３価の鉄化合物を0.1〜８
モル/l含有させるようにする。As the divalent and trivalent iron compounds, chlorides, sulfuric acid compounds and the like can be used, and as a polar solvent for dissolving these iron compounds, the solubility of iron is not impaired and the electrode reaction rate is improved. Therefore, hydrochloric acid or a mixed solution of hydrochloric acid and sulfuric acid is preferable, but hydrobromic acid, a polar organic solvent or the like can be used. In this case, when adjusting the active material on the positive electrode side, for example, a divalent or trivalent iron compound is added in an amount of 0.1 to 8 in hydrochloric acid.
Mol / l.
なお、正極側の活物質の主たる反応化学種が臭素、ヨウ
素、鉄イオンである場合には、塩素が主たる反応化学種
である場合に比べて、起電力は低下するが、電池反応の
充放電過電圧は小さくなり、電池活物質の貯蔵は容易に
なる。しかし、活物質であるハロゲンの全てを臭素また
は／およびヨウ素として使用することは、経済性および
溶解度の点で得策でなく、臭素、ヨウ素を活物質として
使用する場合には可能な限り塩酸（0.1モル/l以上）と
共用することが望ましい。When the main reactive chemical species of the active material on the positive electrode side are bromine, iodine, and iron ions, the electromotive force is lower than when chlorine is the main reactive chemical species, but the charge and discharge of the battery reaction The overvoltage becomes small and the storage of the battery active material becomes easy. However, using all of the halogen as the active material as bromine and / or iodine is not good in terms of economy and solubility, and when using bromine or iodine as the active material, hydrochloric acid (0.1 Mol / l or more).
また、正、負極共に、空隙率85％以下の液透過型炭素多
孔質電極を使用し、電極反応を行わないときは、電解液
を全量タンクに戻して貯蔵するようにすれば、自己放電
を防ぐことができる。Also, for both positive and negative electrodes, liquid-permeable carbon porous electrodes with a porosity of 85% or less are used, and when no electrode reaction is carried out, if the electrolyte solution is returned to the tank and stored, the self-discharge will occur. Can be prevented.
（発明の効果） この発明に係るレドックス電池によれば下記のような効
果が達成できる。(Effect of the Invention) The redox battery according to the present invention can achieve the following effects.
（１）バナジウム３価/2価レドックスイオンの電極反応
の電位は、クロムイオンに比べ正電位側にあるうえ、電
極反応も速いため、負極反応に水素の発生等の副反応が
なく、電池の充放電クーロン効率が高い。更に正極での
ハロゲン乃至鉄の電極反応も速いので、電池の設計、製
作が容易である。(1) The potential of the electrode reaction of vanadium trivalent / valent bivalent redox ions is on the positive potential side compared to chromium ions, and the electrode reaction is fast, so there is no side reaction such as hydrogen generation in the negative electrode reaction, High charge / discharge coulomb efficiency. Furthermore, since the halogen or iron electrode reaction at the positive electrode is fast, the battery can be easily designed and manufactured.
（２）また、この発明によればバナジウム化合物はクロ
ムに比べて硫酸、塩酸等の極性溶媒に対する溶解度が高
いため、負極側の活物質中２価、３価のバナジウム濃度
を高濃度に保つことができ、また正極側の活物質を高濃
度に保ってもバナジウムの極性溶媒に対する溶解度が損
なわれることはない。(2) Further, according to the present invention, since the vanadium compound has a higher solubility in a polar solvent such as sulfuric acid and hydrochloric acid than chromium, it is necessary to maintain a high concentration of divalent or trivalent vanadium in the active material on the negative electrode side. The solubility of vanadium in a polar solvent is not impaired even if the active material on the positive electrode side is kept at a high concentration.
（３）亜鉛、銅、ニッケル、スズ、鉛など充電時、電極
に金属として析出するイオン種を使用する電池に比べ、
この発明に係るレドックス電池は反応種が充放電のいず
れの場合も溶媒中に溶解しているため、電解液貯蔵タン
クの大きさと液中の活物質濃度に依存する電気貯蔵容量
の選択を自由に行なうことができる。(3) Compared to batteries that use ionic species that deposit as metal on the electrodes when charging zinc, copper, nickel, tin, lead, etc.
In the redox battery according to the present invention, since the reactive species are dissolved in the solvent in any case of charge and discharge, the electric storage capacity depending on the size of the electrolytic solution storage tank and the active material concentration in the solution can be freely selected. Can be done.
（４）バナジウムイオンは優れた電気化学的特性を有す
るが、その反面高価であるなどの難点があるが、この発
明に係るレドックス電池では２価、３価のバナジウムイ
オンを負極側にのみ使用し、正極側には安価で、速い電
極反応を示すハロゲン化物イオン、鉄イオンを使用する
ため、正、負極の両方にバナジウムを使用する従来のバ
ナジウムレドックス電池に比べて経済的な負担を半減す
ることができる。(4) Vanadium ions have excellent electrochemical properties, but on the other hand, they are expensive, but in the redox battery according to the present invention, divalent and trivalent vanadium ions are used only on the negative electrode side. Since the positive electrode side uses halide ions and iron ions that are inexpensive and shows a fast electrode reaction, the economic burden is halved compared to the conventional vanadium redox battery that uses vanadium for both the positive and negative electrodes. You can
また、この発明に係るレドックス電池は従来の鉄−クロ
ム−塩酸系レドックス・フロー型電池と同様に薄型の単
電池を積層することによって望みの大きさの電圧に設計
が可能である。Further, the redox battery according to the present invention can be designed to have a desired voltage by stacking thin single cells as in the conventional iron-chromium-hydrochloric acid redox flow type battery.
（実施例） この発明の二次電池（単電池）の一実施例を示す装置を
第１図に示す。電池本体１は、隔膜４の両側に設けられ
たカーボンクロス電極（正極及び負極）3A、3Bと、更に
その外側に設けられたエンドプレート2A、2Bとからな
り、正極液及び負極液は、それぞれライン6A及び6B並び
に正極液タンク5A及び負極液タンク5Bを通ってポンプ7A
及び7Bにより正極3A及び負極3Bに流通させる。(Embodiment) FIG. 1 shows an apparatus showing one embodiment of the secondary battery (unit cell) of the present invention. The battery body 1 is composed of carbon cross electrodes (positive and negative electrodes) 3A and 3B provided on both sides of the diaphragm 4, and end plates 2A and 2B provided further outside thereof, and the positive electrode liquid and the negative electrode liquid are respectively Pump 7A through lines 6A and 6B and positive electrode liquid tank 5A and negative electrode liquid tank 5B
And 7B to distribute to the positive electrode 3A and the negative electrode 3B.
なお、特に塩化物イオンを活物質として使用する場合に
は、電極反応中に生成する塩素を水和物として貯蔵する
ため、正極液タンク5A内を低温に保持することが好まし
く、このためヒートポンプ装置８に連結された熱交換チ
ューブ9A、9Bを正極液タンク5A、負極液タンク5B内に挿
入し、少なくとも充電の一期間中はヒートポンプ装置８
を稼動し、正極側より負極側へ熱を移動させ、例えば負
極液側30〜60℃、正極液側10〜20℃に保持するようにし
てある。In particular, when chloride ions are used as an active material, chlorine generated during the electrode reaction is stored as a hydrate, and therefore it is preferable to keep the positive electrode liquid tank 5A at a low temperature, and therefore a heat pump device is used. The heat exchange tubes 9A and 9B connected to 8 are inserted into the positive electrode liquid tank 5A and the negative electrode liquid tank 5B, and at least during one period of charging, the heat pump device 8
Is operated to transfer heat from the positive electrode side to the negative electrode side, and the heat is maintained at, for example, 30 to 60 ° C. on the negative electrode liquid side and 10 to 20 ° C. on the positive electrode liquid side.
次に、充放電過電圧が小さく、副反応がないバナジウム
−ハロゲン（または鉄）−塩酸（一部硫酸混合）系活物
質電解液を使用して以下に示す実施例を行なった。Next, the following examples were carried out using a vanadium-halogen (or iron) -hydrochloric acid (partially sulfuric acid mixed) active material electrolyte having a small charge / discharge overvoltage and no side reaction.
実施例１ 0.05Mバナジウム３価/2価レドックスイオンが電極反応
する状態を、各種濃度の塩酸中で確認した。Example 1 The state in which 0.05 M vanadium trivalent / valent bivalent redox ions reacted with the electrodes was confirmed in various concentrations of hydrochloric acid.
第２図は、0.05Mバナジウム３価/2価レドックスイオン
が電極反応する状態を、各種濃度の塩酸中で測定したパ
ルス・ポルタンモグラムで、第２図（Ａ）は正逆パルス
・ポーラログラム、第２図（Ｂ）は微分パルス・ポーラ
ログラムであり、その測定条件は第２図（Ａ）において
は掃引速度（Ｖ）:10mV/s、水銀滴下時間（ｔ）:1.0s、
水銀柱高さ（ｈ）:55cm、電極（Ｅ）：滴下水銀電極（D
ME）、第２図（Ｂ）においてはv:10mV/s、t:0.5s、h:55
cm、E:DMEである。Fig. 2 is a pulse voltammogram measured with various concentrations of hydrochloric acid in the state of 0.05M vanadium trivalent / 2 valent redox ion as an electrode reaction. Fig. 2 (A) is a forward / reverse pulse polarogram. , FIG. 2 (B) is a differential pulse polarogram, and the measurement conditions are as shown in FIG. 2 (A): sweep speed (V): 10 mV / s, mercury dropping time (t): 1.0 s,
Height of mercury column (h): 55 cm, Electrode (E): Dropping mercury electrode (D
ME) and Fig. 2 (B), v: 10mV / s, t: 0.5s, h: 55
cm, E: DME.
その結果、第２図に示したように、当該バナジウムイオ
ンのレドックス反応の可逆性は、塩酸濃度と共に良好と
なることが明らかとなった。As a result, as shown in FIG. 2, it was clarified that the reversibility of the redox reaction of the vanadium ion was improved with the concentration of hydrochloric acid.
実施例２ 0.05M（mol/dm-3）臭化水素酸と2Mの硫酸混合液に、0.0
5Mの三塩化バナジウムを溶解した電池活物質電解液の炭
素電極上でのサイクリック・ボルタンモグラム（CV曲
線）を第３図に示す。その測定条件はE:グラファイト強
化炭素（GRC）、v:200mV/sであり、この結果硫酸中でバ
ナジウム−臭素系およびバナジウム−塩素系の電位差
は、各々約1.5V、1.2Vであった。Example 2 A mixture of 0.05M (mol / dm −3 ) hydrobromic acid and 2M sulfuric acid was mixed with 0.0
FIG. 3 shows a cyclic voltammogram (CV curve) on the carbon electrode of the battery active material electrolyte in which 5M vanadium trichloride was dissolved. The measurement conditions were E: graphite-reinforced carbon (GRC), v: 200 mV / s. As a result, the potential difference between vanadium-bromine system and vanadium-chlorine system in sulfuric acid was about 1.5 V and 1.2 V, respectively.
実施例３ 4M塩酸中に0.05M三塩化バナジウムと0.05M塩化第一鉄溶
液の炭素電極上でのCV曲線（実線）とこれに0.9M硫酸を
混合使用した場合のCV曲線（破線）を第４図に示す。そ
の測定条件はv:200mV/s、E:GRC、感度:10mA/V、このCV
曲線によれば、Ｖ−Cl系、Ｖ−Fe系の電位差は、各々約
1.45V、0.9Vであった。また、硫酸を混合使用するとバ
ナジウムのレドックス反応の可逆性が向上した。Example 3 A CV curve (solid line) on a carbon electrode of 0.05M vanadium trichloride and 0.05M ferrous chloride solution in 4M hydrochloric acid and a CV curve (broken line) when 0.9M sulfuric acid is mixed and used are shown in FIG. It is shown in FIG. The measurement conditions are v: 200 mV / s, E: GRC, sensitivity: 10 mA / V, this CV
According to the curve, the potential difference between V-Cl system and V-Fe system is about
It was 1.45V and 0.9V. Moreover, the reversibility of the redox reaction of vanadium was improved when sulfuric acid was mixed and used.
実施例４、５ 第１図に示す電池で、下記の条件で電池反応を行なわせ
た結果を、第１表に示す。Examples 4 and 5 Table 1 shows the results of the battery reaction carried out under the following conditions with the batteries shown in FIG.
第１図は、この発明の電池反応を行なわせたレドックス
二次電池の一例の概念図、第２図は0.05Mバナジウム３
価/2価レドックスイオンが電極反応する状態を、各種濃
度の塩酸中で測定したパルス・ボルタンモグラム、第２
図（Ａ）は正逆パルス・ポーラログラム、第２図（Ｂ）
は微分パルス・ポーラログラムであり、第３図は、0.05
M臭化水素酸と2Mの硫酸混合液に、0.05Mの三塩化バナジ
ウムを溶解した電池活物質電解液の炭素電極上でのサイ
クリック・ボルタモグラム、第４図は7M塩酸中に0.05M
三塩化バナジウムと0.05M塩化第１鉄溶液の炭素電極上
でのサイクリック・ボルタンモグラムである。 図中、１は単電池本体、2A、2Bは正、負極エンドプレー
ト、3A、3Bは正、負電極カーボンクロス電極、４は隔
膜、5A、5Bは正、負極タンク、6A、6Bは正、負極液ライ
ン、7A、7Bはポンプ、８はヒートポンプ装置、9A、9Bは
熱交換用チューブ。FIG. 1 is a conceptual diagram of an example of a redox secondary battery in which the battery reaction of the present invention is performed, and FIG. 2 is 0.05M vanadium 3
Pulse voltammograms of the state of valence / 2 valence redox ions reacting in the electrode in various concentrations of hydrochloric acid, second
Figure (A) is a forward and reverse pulse polarogram, Figure 2 (B)
Is the differential pulse polarogram, and Fig. 3 shows 0.05
Cyclic voltammogram of a battery active material electrolyte prepared by dissolving 0.05M vanadium trichloride in a mixed solution of M hydrobromic acid and 2M sulfuric acid on a carbon electrode. Fig. 4 shows 0.05M in 7M hydrochloric acid.
It is a cyclic voltammogram on the carbon electrode of vanadium trichloride and a 0.05M ferrous chloride solution. In the figure, 1 is a battery body, 2A and 2B are positive, negative electrode end plates, 3A and 3B are positive, negative electrode carbon cross electrode, 4 is a diaphragm, 5A and 5B are positive, negative electrode tanks, 6A and 6B are positive, Anode liquid line, 7A and 7B are pumps, 8 is a heat pump device, and 9A and 9B are heat exchange tubes.
Claims (5)
中に溶解させたバナジウム２価、３価の溶液で構成し、
レドックス対の正極側の活物質をハロゲン、ハロゲンイ
オンの溶液で構成し、該レドックス対を液透過型の電解
槽に送液して充放電を行なわせることを特徴とするレド
ックス電池。1. An active material on the negative electrode side of a redox couple is composed of a solution of vanadium divalent and trivalent, which is dissolved in a polar solvent,
A redox battery characterized in that the active material on the positive electrode side of the redox pair is composed of a solution of halogen and a halogen ion, and the redox pair is fed to a liquid-permeable electrolytic cell for charging and discharging.
中に溶解させたバナジウム２価、３価の溶液で構成し、
レドックス対の正極側の活物質を極性溶媒中に溶解させ
た鉄２価、３価の溶液で構成し、該レドックス対を液透
過型の電解槽に送液して充放電を行なわせることを特徴
とするレドックス電池。2. An active material on the negative electrode side of a redox couple is constituted by a solution of vanadium divalent or trivalent dissolved in a polar solvent,
The active material on the positive electrode side of the redox pair is composed of a divalent or trivalent iron solution dissolved in a polar solvent, and the redox pair is sent to a liquid-permeable electrolytic cell for charging and discharging. Characteristic redox battery.
酸の混合液を使用する特許請求の範囲第１項又は第２項
記載のレドックス電池。3. The redox battery according to claim 1, wherein sulfuric acid or a mixed solution of sulfuric acid and hydrochloric acid is used as the polar solvent on the negative electrode side.
酸の混合液を使用する特許請求の範囲第２項記載のレド
ックス電池。4. The redox battery according to claim 2, wherein hydrochloric acid or a mixed solution of hydrochloric acid and sulfuric acid is used as the polar solvent on the positive electrode side.
合、負極活物質と正極活物質とをそれぞれ貯蔵する溶液
間に熱の移動を行なわしめる装置を設け、少なくとも充
電の一定期間中は該熱移動装置を稼動し、正極活物質よ
り負極活物質へ熱を移動せしめるように構成した特許請
求の範囲第１項記載のレドックス電池。5. When chloride ion is used as the active material on the positive electrode side, a device for transferring heat between the solutions storing the negative electrode active material and the positive electrode active material is provided, and at least during a certain period of charging. The redox battery according to claim 1, wherein the heat transfer device is operated to transfer heat from the positive electrode active material to the negative electrode active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2121764A JPH0758625B2 (en) | 1990-05-11 | 1990-05-11 | Redox battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2121764A JPH0758625B2 (en) | 1990-05-11 | 1990-05-11 | Redox battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0419966A JPH0419966A (en) | 1992-01-23 |
| JPH0758625B2 true JPH0758625B2 (en) | 1995-06-21 |
Family
ID=14819310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2121764A Expired - Lifetime JPH0758625B2 (en) | 1990-05-11 | 1990-05-11 | Redox battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0758625B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2622675A1 (en) | 2010-09-28 | 2013-08-07 | Battelle Memorial Institute | Redox flow batteries based on supporting solutions containing chloride |
| US8916281B2 (en) | 2011-03-29 | 2014-12-23 | Enervault Corporation | Rebalancing electrolytes in redox flow battery systems |
| US8980454B2 (en) | 2013-03-15 | 2015-03-17 | Enervault Corporation | Systems and methods for rebalancing redox flow battery electrolytes |
| US8993183B2 (en) | 2012-12-31 | 2015-03-31 | Enervault Corporation | Operating a redox flow battery with a negative electrolyte imbalance |
| US10673090B2 (en) | 2014-10-06 | 2020-06-02 | Battelle Memorial Institute | All-vanadium sulfate acid redox flow battery system |
| US11557786B2 (en) | 2018-10-01 | 2023-01-17 | President And Fellows Of Harvard College | Extending the lifetime of organic flow batteries via redox state management |
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|---|---|---|---|---|
| JP4863172B2 (en) * | 2010-04-27 | 2012-01-25 | 住友電気工業株式会社 | Redox flow battery |
| DK2581976T3 (en) * | 2010-04-27 | 2014-05-12 | Sumitomo Electric Industries | Redox flow battery |
| US8771856B2 (en) | 2010-09-28 | 2014-07-08 | Battelle Memorial Institute | Fe-V redox flow batteries |
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| WO2018198252A1 (en) * | 2017-04-26 | 2018-11-01 | 日立化成株式会社 | Secondary battery, secondary battery system, and electricity-generating system |
| US11724980B2 (en) | 2018-02-09 | 2023-08-15 | President And Fellows Of Harvard College | Quinones having high capacity retention for use as electrolytes in aqueous redox flow batteries |
| CN114497666B (en) * | 2022-01-19 | 2025-09-05 | 华秦储能技术有限公司 | A method for preparing an electrolyte for an all-vanadium redox flow battery using ferrous sulfide as a reducing agent |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2622675A1 (en) | 2010-09-28 | 2013-08-07 | Battelle Memorial Institute | Redox flow batteries based on supporting solutions containing chloride |
| US9819039B2 (en) | 2010-09-28 | 2017-11-14 | Battelle Memorial Institute | Redox flow batteries based on supporting solutions containing chloride |
| US8916281B2 (en) | 2011-03-29 | 2014-12-23 | Enervault Corporation | Rebalancing electrolytes in redox flow battery systems |
| US8993183B2 (en) | 2012-12-31 | 2015-03-31 | Enervault Corporation | Operating a redox flow battery with a negative electrolyte imbalance |
| US8980454B2 (en) | 2013-03-15 | 2015-03-17 | Enervault Corporation | Systems and methods for rebalancing redox flow battery electrolytes |
| US10673090B2 (en) | 2014-10-06 | 2020-06-02 | Battelle Memorial Institute | All-vanadium sulfate acid redox flow battery system |
| US11532832B2 (en) | 2014-10-06 | 2022-12-20 | Battelle Memorial Institute | All-vanadium sulfate acid redox flow battery system |
| US11557786B2 (en) | 2018-10-01 | 2023-01-17 | President And Fellows Of Harvard College | Extending the lifetime of organic flow batteries via redox state management |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0419966A (en) | 1992-01-23 |
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