JPH07101615B2 - Redox type secondary battery - Google Patents
Redox type secondary batteryInfo
- Publication number
- JPH07101615B2 JPH07101615B2 JP3074808A JP7480891A JPH07101615B2 JP H07101615 B2 JPH07101615 B2 JP H07101615B2 JP 3074808 A JP3074808 A JP 3074808A JP 7480891 A JP7480891 A JP 7480891A JP H07101615 B2 JPH07101615 B2 JP H07101615B2
- Authority
- JP
- Japan
- Prior art keywords
- redox
- vanadium
- sulfuric acid
- battery
- secondary battery
- 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
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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
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- Fuel Cell (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、バナジウム（２価／
３価）−バナジウム（５価／４価）をレドックス対とす
るレドックス型二次電池（以下、レドックス電池と略記
する）に関するものである。This invention relates to vanadium (divalent /
The present invention relates to a redox type secondary battery (hereinafter abbreviated as redox battery) having a redox pair of (trivalent) -vanadium (pentavalent / tetravalent).
【０００２】[0002]
【従来の技術】レドックス電池は、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ながら、電池
活物質の酸化還元反応を利用して充放電を行なうもので
あるが、このレドックス電池は従来の二次電池と比べて
(1) 電解槽自体はそのままにして活物質量を増加させる
だけで蓄電容量を大きくすることができる、(2) 正、負
極活物質は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、(3) 活物質イオンの充放電反応（電極
反応）が単に電池表面で電子の交換であるので、活物質
が電極表面に析出することもないなどの特徴があり、近
年多くのレドックス対について実用化の試みがなされて
いる。2. Description of the Related Art A redox battery is one in which liquid positive and negative battery active materials are circulated in a liquid-permeable type electrolytic cell while charging and discharging utilizing the redox reaction of the battery active material. This redox battery compared to conventional rechargeable batteries
(1) The storage capacity can be increased simply by increasing the amount of active material while leaving the electrolytic cell itself as it is. (2) Positive and negative electrode active materials can be completely separated and stored in a container. Unlike a battery that is in contact with the electrode, the possibility of self-discharge is small. (3) Since the charge / discharge reaction (electrode reaction) of the active material ion is simply the exchange of electrons on the battery surface, the active material is the electrode surface. It is characterized in that it does not precipitate on the surface, and in recent years many redox couples have been tried for practical use.
【０００３】現在実用化段階にあるレドックス電池に
は、クロム２価、３価対鉄２価、３価系をレドックス対
とするレドックス電池がある。このレドックス電池は使
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。Among redox batteries currently in practical use is a redox battery in which a redox pair is a divalent chromium / trivalent iron vs. iron divalent / trivalent system. This redox battery is a battery with 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 as a result both active materials are Since it becomes a mixed liquid of iron and chromium, and it is subject to solubility restrictions,
Cannot be a concentrated solution.
【０００４】また、クロム、鉄系のレドックス電池の場
合、異種のレドックスイオンで長期の充放電を繰り返す
と、隔膜を相互のイオンが通過して電流効率を低下し、
最終的には出力電圧が単セルあたり0.9 〜1V程度、電池
のエネルギー密度は30ワットアワ-/リットル 程度にしかならない
などの問題点がある。Also, in the case of chromium and iron redox batteries, when repeated charging and discharging are repeated with different kinds of redox ions, mutual ions pass through the diaphragm and current efficiency decreases,
Finally, there are problems that the output voltage is about 0.9-1V per cell and the energy density of the battery is only about 30 watt-hour / liter.
【０００５】一方、この欠点を改善するレドックス電池
としてクロム−塩素系のレドックス対等を用いたレドッ
クス電池が提案されている（特願昭61-24172号) 。しか
し、このクロム、塩素系をレドックス対とするレドック
ス電池では、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し、しかもクロム２価／３価イ
オンのレドックス電位は水素発生電位に近いため、酸が
高濃度となるほど、水素ガス発生の副反応が増大し、効
率低下の原因になる。更に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などの欠点があ
る。On the other hand, a redox battery using a chromium-chlorine redox pair or the like has been proposed as a redox battery for improving this drawback (Japanese Patent Application No. 61-24172). However, this redox battery using a chromium- and chlorine-based redox pair uses chlorine as an active material, and therefore requires a high concentration of chloride ions, and the redox potential of the divalent / trivalent chromium ions is the hydrogen generation potential. Therefore, as the concentration of acid increases, the side reaction of hydrogen gas generation increases, which causes a decrease in efficiency. Further, there is a drawback that the solubility of chromium ions is reduced due to the coexistence of high concentration chloride ions.
【０００６】また、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がなされているが(
特願昭60-207258 号) 、いずれの組合せも単電池当たり
の起電力が小さかったり、電極へ金属が析出する複雑な
電池反応であったり、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 (
Japanese Patent Application No. 60-207258), all combinations have advantages and disadvantages such as a small electromotive force per cell and a complicated cell reaction in which metal is deposited on the electrodes.
【０００７】これに対して、正極活物質として4 /5価の
バナジウム、負極活物質として3/2価系のバナジウムを
使用し、更に電解液として1 〜5モル/リットル(M)の硫酸溶液
を使用した全バナジウムレドックス電池が提案されてい
る[J.Power Sources,15 179,16 85(1985),J.Electroche
m.Soc.,133 1057(1986)、特開昭62-186473 号]。On the other hand, 4/5 valent vanadium is used as the positive electrode active material and 3/2 valent vanadium is used as the negative electrode active material, and 1 to 5 mol / liter (M) sulfuric acid solution is further used as the electrolytic solution. An all-vanadium redox battery has been proposed [J. Power Sources, 15 179,16 85 (1985), J. Electroche
m.Soc., 133 1057 (1986), JP-A-62-186473].
【０００８】[0008]
【発明が解決しようとする問題点】しかし、このレドッ
クス電池において使用する1 〜5M硫酸濃度の電解液で
は、負極活物質のバナジウム3/2価系に比べて正極活物
質のバナジウム4/5 価のレドックス反応が遅いため、充
放電電圧の差が大きく、充放電効率向上の妨げになって
いた。[Problems to be Solved by the Invention] However, with the electrolyte solution of 1 to 5 M sulfuric acid concentration used in this redox battery, the vanadium 4/5 valence of the positive electrode active material is higher than that of the vanadium 3/2 valence system of the negative electrode active material. Due to the slow redox reaction, the difference in charge / discharge voltage was large, which hindered improvement of charge / discharge efficiency.
【０００９】これに対して、実用電池では経済上エネル
ギー効率90% 以上が必要であり、このためには電流効率
と電圧効率を95% 以上とする必要があるが、上述のレド
ックス電池に代表されるこれまでの全バナジウムレドッ
クス電池では、正極活物質の電池反応速度が遅いため、
電圧効率が90% 止まりであり、したがって電流効率も90
% 前後であり、その結果電流効率と電圧効率の積である
エネルギー効率は良くて81% 程度であった。On the other hand, a practical battery is required to have an energy efficiency of 90% or more in economic terms, and for this purpose, current efficiency and voltage efficiency must be 95% or more. In all vanadium redox batteries up to now, since the battery reaction rate of the positive electrode active material is slow,
The voltage efficiency remains at 90% and therefore the current efficiency is 90%.
The energy efficiency, which is the product of current efficiency and voltage efficiency, was about 81% at the best.
【００１０】なお、全バナジウムレドックス電池の電圧
効率並びに電流効率を実用上95% 以上に高めるために
は、電池の電解液としてバナジウムの充、放電（酸化、
還元反応）が各々、拡散律速かそれに近い反応速度で進
行する電解液を使用する必要がある。In order to increase the voltage efficiency and current efficiency of all vanadium redox batteries to 95% or more in practical use, charging and discharging (oxidation, oxidation, etc.) of vanadium as the battery electrolyte is performed.
It is necessary to use an electrolytic solution in which each reduction reaction) progresses at a reaction rate that is at or near the diffusion rate.
【００１１】そこで、本願発明者らはこのような電解液
を得るために鋭意研究の結果、全バナジウムレドックス
電池の電解液として、電解液中でバナジウムイオンのサ
イクリックボルタンモグラムを描き、酸化波と還元波の
ピーク電位差が150mV(酸化反応電位と還元反応電位の
差）以下になる正、負極液を使用する必要があることを
見出したものである。The inventors of the present invention have conducted extensive studies to obtain such an electrolytic solution, and as a result, as an electrolytic solution for an all-vanadium redox battery, a cyclic voltammogram of vanadium ions is drawn in the electrolytic solution to obtain an oxidation wave. It was found that it is necessary to use positive and negative electrode liquids in which the peak potential difference of the reduction wave is 150 mV or less (difference between oxidation reaction potential and reduction reaction potential).
【００１２】[0012]
【問題点を解決するための手段】そこで、この発明は上
記知見に基づいて、負極側の活物質をバナジウム3/2 価
系、正極側の活物質をバナジウム4/5 価系のレドックス
対で構成されるレドックス電池において、上記両活物質
の各バナジウムイオンを溶解する電解液中で、バナジウ
ムイオンのサイクリックボルタンモグラムの酸化波と還
元波のピーク電位差が150mV 以下となるような電解液を
用いることを提案するものである。[Means for Solving the Problems] Based on the above findings, the present invention is based on the fact that the negative electrode active material is a vanadium 3 / 2-valent redox pair and the positive electrode active material is a vanadium 4 / 5-valent redox couple. In the redox battery that is composed, in the electrolyte that dissolves each vanadium ion of both active materials, use an electrolyte that has a peak potential difference of 150 mV or less between the oxidation wave and the reduction wave of the cyclic voltammogram of vanadium ions. It is proposed to use.
【００１３】ここで、バナジウムイオンのサイクリック
ボルタンモグラムの酸化波と還元波のピーク電位差が15
0mV 以下としたのは、ピーク電位差が150mV 以上では実
用的な充放電エネルギー効率のものが得られないためで
ある。なお、上述のピーク電位差は酸化反応と還元反応
の完全に拡散律速の場合それは60mVで、それ以下にはな
らない。Here, the peak potential difference between the oxidation wave and the reduction wave of the cyclic voltammogram of vanadium ion is 15
The reason for setting it to 0 mV or less is that a practical charge / discharge energy efficiency cannot be obtained when the peak potential difference is 150 mV or more. In addition, the above-mentioned peak potential difference is 60 mV in the case where the oxidation reaction and the reduction reaction are completely diffusion-controlled, and does not become lower than that.
【００１４】なお、このような電解液の一例としては、
硫酸を6M以上含有した溶液を挙げることができる。As an example of such an electrolytic solution,
A solution containing 6 M or more of sulfuric acid can be mentioned.
【００１５】ここで、電解液の硫酸濃度を6M以上とした
のは、本願発明者らの研究によれば正極でのバナジウム
4/5 価系の反応速度が硫酸の濃度6M以上で拡散律速とな
り、電極上で極めて良好で、且つ速い電極反応が進行す
るためである。According to the research conducted by the inventors of the present invention, the sulfuric acid concentration of the electrolytic solution is set to 6 M or more.
This is because the reaction rate of the 4/5 valent system becomes diffusion-controlled when the concentration of sulfuric acid is 6 M or more, and the electrode reaction is extremely good and fast on the electrode.
【００１６】この結果、硫酸濃度6M以上含有する電解液
を使用すると、正極でのバナジウム4/5 価のレドックス
反応が負極でのバナジウム3/2 価のレドックス反応とほ
ぼ等速で進行する。As a result, when an electrolytic solution containing sulfuric acid at a concentration of 6 M or more is used, the vanadium 4/5 valent redox reaction at the positive electrode proceeds almost at the same speed as the vanadium 3/2 valent redox reaction at the negative electrode.
【００１７】一方、高濃度硫酸中での負極のバナジウム
2/3 価系のレドックス反応は、硫酸濃度に殆ど関係なく
良好に進行する。On the other hand, vanadium for the negative electrode in high-concentration sulfuric acid
The 2 / 3-valent redox reaction proceeds well regardless of the sulfuric acid concentration.
【００１８】即ち、この発明において上述のような全バ
ナジウムレドック電池において硫酸濃度6M以上含有する
電解液を使用することは、バナジウム2/3 価のレドック
ス反応に影響を及ぼさずに、バナジウム4/5 価の反応速
度を高めるために極めて有効な手段である。That is, in the present invention, the use of an electrolytic solution containing sulfuric acid concentration of 6M or more in the above-mentioned all-vanadium redock battery does not affect the vanadium 2 / 3-valent redox reaction, and the vanadium 4 / It is an extremely effective means for increasing the pentavalent reaction rate.
【００１９】なお、この電極反応の速度は炭素電極への
硫酸イオンのインターカレーションが顕著になる硫酸濃
度まで続く。The rate of this electrode reaction continues until the sulfuric acid concentration at which the intercalation of sulfate ions to the carbon electrode becomes remarkable.
【００２０】炭素電極への硫酸イオンのインターカレー
ションが顕著になる硫酸濃度は、炭素電極の種類により
著しく異なる。The sulfuric acid concentration at which the intercalation of sulfate ions into the carbon electrode becomes remarkable depends on the type of carbon electrode.
【００２１】グラファイト成分の多い炭素材を使用した
炭素電極ほど低硫酸濃度で硫酸イオンのインターカレー
ションが顕著となる傾向が見られ、グラファイト成分85
% である炭素電極を用いた場合、硫酸イオンのインター
カレーションは硫酸濃度9Mで観察される。A carbon electrode using a carbon material having a large amount of graphite component tends to show more remarkable intercalation of sulfate ions at a lower sulfuric acid concentration.
When using a carbon electrode, which is%, the intercalation of sulfate ions is observed at a sulfuric acid concentration of 9M.
【００２２】しかし、グラファイト化の低い炭素繊維電
極では更に高濃度の硫酸中でも使用可能と予想される。
なお、硫酸濃度の上限は液透過型炭素多孔質電極（主に
炭素繊維電極）に硫酸イオンのインターカレーションが
顕著となる10M 濃度程度である。However, it is expected that the carbon fiber electrode having low graphitization can be used even in a high concentration of sulfuric acid.
The upper limit of the sulfuric acid concentration is about 10M concentration at which the intercalation of sulfate ion becomes remarkable in the liquid-permeable carbon porous electrode (mainly carbon fiber electrode).
【００２３】一方、隔膜として使用している陽イオン交
換膜による膜抵抗は硫酸濃度への依存性が小さく、硫酸
濃度の影響を殆ど受けない。On the other hand, the membrane resistance of the cation exchange membrane used as the diaphragm has little dependency on the sulfuric acid concentration and is hardly affected by the sulfuric acid concentration.
【００２４】更に、電解液中の硫酸濃度の増加は電解液
の粘度増加を伴うため、電解液を循環させるためには好
ましくないが、このような場合には液間欠静止型の電解
槽を使用すればよい。Further, an increase in the sulfuric acid concentration in the electrolytic solution is not preferable for circulating the electrolytic solution because it increases the viscosity of the electrolytic solution, but in such a case, an intermittent stationary electrolytic cell is used. do it.
【００２５】[0025]
【発明の効果】以上要するに、この発明によれば負極側
の活物質をバナジウム3/2 価系、正極側の活物質をバナ
ジウム4/5 価系のレドックス対で構成されるレドックス
電池において、上記両活物質の各バナジウムイオンを溶
解した電解液として、この電解液中でバナジウムイオン
のサイクリックボルタンモグラムを描き、酸化波と還元
波のピーク電位差が150mV 以下になる正、負極液を使用
するすることにより、 電池反応の電圧効率並びに電流効
率を向上させることができ、実用的な全バナジウムレド
ックス電池のエネルギー効率を得ることができた。In summary, according to the present invention, in the redox battery in which the active material on the negative electrode side is a vanadium 3/2 valent redox pair and the active material on the positive electrode side is a vanadium 4/5 valent redox pair, As an electrolyte solution in which each vanadium ion of both active materials is dissolved, draw a cyclic voltammogram of vanadium ions in this electrolyte solution, and use positive and negative electrode solutions in which the peak potential difference between the oxidation wave and the reduction wave is 150 mV or less. By doing so, the voltage efficiency and current efficiency of the battery reaction could be improved, and the practical energy efficiency of the all-vanadium redox battery could be obtained.
【００２６】また、この発明によれば上述のような電解
液は、例えば硫酸濃度6M以上含有する溶液により得るこ
とができるため、短時間率高性能レドックス電池の製作
が極めて容易に行なうことができる。Further, according to the present invention, the electrolytic solution as described above can be obtained, for example, by a solution containing a sulfuric acid concentration of 6 M or more, so that a high-performance redox battery having a short time rate can be manufactured very easily. .
【００２７】一方、バナジウム３、４、５価レドックス
イオンはクロム２価、鉄２価イオンに比べ、硫酸中に良
く溶解する。On the other hand, vanadium 3, 4, and 5 valent redox ions dissolve better in sulfuric acid than chromium divalent and iron divalent ions.
【００２８】なお、一般にバナジウム５価化合物は硫酸
に溶解し難いが、一旦溶解したバナジウム４価イオンは
硫酸中で酸化されて５価イオンとなっても沈殿しないの
で、この発明ではバナジウムが反応途中で晶析すること
が殆どない。Generally, a vanadium pentavalent compound is difficult to dissolve in sulfuric acid, but once dissolved vanadium tetravalent ion does not precipitate even if it is oxidized in sulfuric acid to form a pentavalent ion. Almost no crystallization occurs.
【００２９】また、バナジウムが反応途中で晶析するよ
うな場合には、電解液の温度を制御して一旦晶析したバ
ナジウムを溶解させるようにすれば良い。When vanadium is crystallized during the reaction, the temperature of the electrolytic solution may be controlled to dissolve the once crystallized vanadium.
【００３０】[0030]
【実施例】以下、この発明の実施例を示す。 実施例１ 図１は2 〜8M H2SO4含有する溶液を電解液として、この
電解液中における0.05M バナジウム4/5 価レドックスイ
オンのサイクリックボルタンモグラム（ＣＶ曲線）であ
る。同図において、サイクリックボルタンモグラムの酸
化波ａと還元波ｂのピーク電位差ΔＥは3M H2SO4 含有
電解液を使用した場合には200mV 程度であったが、6 〜
8M H2SO4 含有電解液の場合には60mV程度となった。 そ
して、H2SO4 含有6M以上の電解液を使用することによっ
て電池の電極反応が著しく良好となることが明かとなっ
た。EXAMPLES Examples of the present invention will be shown below. Example 1 FIG. 1 is a cyclic voltammogram (CV curve) of 0.05M vanadium 4/5 valent redox ion in this electrolytic solution using a solution containing 2 to 8M H 2 SO 4 . In the figure, the peak potential difference ΔE between the oxidation wave a and the reduction wave b of the cyclic voltammogram was about 200 mV when the electrolyte containing 3M H 2 SO 4 was used.
In the case of the electrolyte containing 8M H 2 SO 4 , it was about 60 mV. Then, it was revealed that the electrode reaction of the battery was remarkably improved by using the electrolytic solution containing H 2 SO 4 containing 6 M or more.
【００３１】実施例２ ＧＲＣ(Graphite reinforcement carbon, シャープペン
シル芯、グラファイト含有率85%)電極上で9M硫酸のみと
9M硫酸中に0.05M バナジウムイオンを溶解した溶液との
ＣＶ曲線を求めた。その結果を図２に示す。このＣＶ曲
線によれば、9M硫酸のみの場合に硫酸のインターカレー
ションと考えられるピークが観察され、バナジウムの共
存する溶液中でバナジウムのレドックス反応のピークが
インターカレーションのピークと還元方向で重なってい
ることが観察できる。Example 2 On a GRC (Graphite reinforcement carbon, mechanical pencil core, graphite content 85%) electrode, only 9M sulfuric acid was used.
A CV curve was obtained with a solution of 0.05M vanadium ion dissolved in 9M sulfuric acid. The result is shown in FIG. According to this CV curve, a peak considered to be sulfuric acid intercalation was observed when only 9M sulfuric acid was used, and the redox reaction peak of vanadium overlaps with the intercalation peak in the reducing direction in the solution in which vanadium coexists. Can be observed.
【００３２】実施例３ また、この発明に係るレドックス電池（単電池）の一実
施例を示す装置を図３に示す。これによれば、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 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3Bに流
通されるようになっている。また、晶析の制御のための
熱交換機８とチューブ9A,9B が備えられる。Embodiment 3 FIG. 3 shows an apparatus showing an embodiment of the redox battery (single battery) according to the present invention. According to this, the battery main body 1 is composed of carbon cloth 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. Are circulated to the positive electrodes 3A and 3B by the pumps 7A and 7B through the lines 6A and 6B, the positive electrode liquid tank 5A and the negative electrode liquid tank 5B, respectively. Further, a heat exchanger 8 and tubes 9A and 9B for controlling crystallization are provided.
【００３３】実施例４ 上記硫酸濃度7.2Mの場合の充電曲線ｃ，放電曲線ｄを図
４に示す。なお、同図には充電曲線ｃと放電曲線ｄにそ
れぞれの開回路電圧の曲線ｃ1 とｄ1 を点線で同時に示
してある。この上下２本の曲線の電圧差（拡散律速に近
い場合のサイクリックボルタンモグラムの酸化波または
還元波のピーク電位差に相当する電圧差）が充電反応と
放電反応のそれぞれの反応速度の程度を示しており、こ
の幅が広くなればなるほど充電は高い電圧で行なわなけ
ればならず、逆に放電は低い電圧で起きることになり、
電圧効率が悪くなるが、同図によればこの電圧差は80mV
である。これは上記硫酸濃度7.2Mの溶液が本発明に使用
する電解液の範囲にあることを示している。Example 4 FIG. 4 shows the charge curve c and the discharge curve d in the case of the above sulfuric acid concentration of 7.2M. In the same figure, the curves c 1 and d 1 of the open circuit voltage are shown in the charging curve c and the discharging curve d at the same time by dotted lines. The voltage difference between the upper and lower curves (the voltage difference corresponding to the peak potential difference of the oxidation wave or the reduction wave of the cyclic voltammogram when the diffusion rate is close) determines the degree of the reaction rate of each of the charge reaction and the discharge reaction. It is shown that the wider this width is, the higher the voltage needs to be charged, and conversely, the lower voltage is used for the discharge.
Although the voltage efficiency is poor, the voltage difference is 80mV according to the figure.
Is. This indicates that the solution having a sulfuric acid concentration of 7.2 M is within the range of the electrolytic solution used in the present invention.
【００３４】下記表１に、図３に示したレドックス電池
を使用して充放電を行なった場合の実験条件とその結果
を示す。ここで、実験条件Ａは硫酸濃度3Mを使用し、公
知刊行物[M.Kazacos and M.Skyllas Kazacos,J.Elector
ochem.Soc.,136 2759(1989):オーストラリア実験] に記
載されている条件の比較例、実験条件Ｂ（本発明実験）
は実施例４の硫酸濃度7.2Mを電解液として使用したこの
発明に係る実施例である。Table 1 below shows the experimental conditions and results when charging and discharging were performed using the redox battery shown in FIG. Here, the experimental condition A uses a sulfuric acid concentration of 3 M, and uses a known publication [M. Kazacos and M. Skyllas Kazacos, J. Elector.
ochem.Soc., 136 2759 (1989): Australian experiment], comparative example of experimental conditions, experimental condition B (invention experiment)
Is an example according to the present invention in which the sulfuric acid concentration of 7.2 M of Example 4 was used as an electrolytic solution.
【００３５】[0035]
【表１】 [Table 1]
【００３６】この結果、硫酸濃度3Mの比較例に比べて硫
酸濃度7.2Mのこの発明の実施例においては電池の内部抵
抗が低く、充放電エネルギー効率が優れた結果が得られ
た。As a result, in the example of the present invention having a sulfuric acid concentration of 7.2 M, the internal resistance of the battery was low and the charge and discharge energy efficiency was excellent as compared with the comparative example having a sulfuric acid concentration of 3 M.
【図１】図１は、0.05M バナジウム4/5 価レドックスイ
オンが電極反応する状態を、硫酸濃度2M、3M の場合( 比
較例）と硫酸濃度6 〜8M中で測定したサイクリックボル
タンモグラムである。FIG. 1 shows cyclic voltammograms of 0.05M vanadium 4 / 5-valent redox ion in the state of electrode reaction when the sulfuric acid concentration was 2M and 3M (comparative example) and the sulfuric acid concentration was 6 to 8M. Is.
【図２】図２は、0.05M バナジウムイオンを9M硫酸に溶
解した溶液と9M硫酸のみの溶液中でＧＲＣ炭素電極上で
求めたサイクリックボルタンモグラムである。FIG. 2 is a cyclic voltammogram obtained on a GRC carbon electrode in a solution of 0.05M vanadium ion dissolved in 9M sulfuric acid and a solution of 9M sulfuric acid alone.
【図３】図３は、この発明の電池反応を行わせたレドッ
クス電池の一例を示す概念図である。FIG. 3 is a conceptual diagram showing an example of a redox battery in which the battery reaction of the present invention is performed.
【図４】図４は、硫酸濃度7.2M含有の溶液を電解液とし
て充、放電を行なった場合の充、放電曲線である。FIG. 4 is a charging / discharging curve when a solution containing a sulfuric acid concentration of 7.2 M was charged and discharged as an electrolytic solution.
１ 単電池本体 2A,2B 正、負極エンドプレート 3A,3B 正、負極カーボンクロス電極 ４ 隔膜 5A,5B 正、負極タンク 6A,6B 正、負極ライン 7A,7B ポンプ ８ ヒートポンプ装置 9A,9B 熱交換用チューブ 1 Cell main body 2A, 2B positive, negative electrode end plate 3A, 3B positive, negative electrode carbon cross electrode 4 diaphragm 5A, 5B positive, negative electrode tank 6A, 6B positive, negative electrode line 7A, 7B pump 8 heat pump device 9A, 9B for heat exchange tube
───────────────────────────────────────────────────── フロントページの続き (72)発明者 黒川 浩助 茨城県つくば市梅園１丁目１番４ 工業技 術院電子技術総合研究所内 (56)参考文献 特開 昭62−186473（ＪＰ，Ａ) 特開 昭64−60967（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kosuke Kurokawa 1-4, Umezono, Tsukuba-shi, Ibaraki Electronic Technology Research Institute, Industrial Technology Institute (56) Reference JP-A-62-186473 (JP, A) Japanese Patent Laid-Open No. 64-60967 (JP, A)
Claims (3)
の溶液、正極側の活物質をバナジウム４価、５価の溶液
とするレドックス対で構成されたレドックス型二次電池
において、上記両活物質の各バナジウムイオンを溶解す
る電解液として硫酸含有６Ｍ以上の電解液を用いること
を特徴とするレドックス型二次電池。1. A redox type secondary battery comprising a redox pair, wherein the negative electrode active material is a vanadium divalent or trivalent solution and the positive electrode active material is a vanadium tetravalent or pentavalent solution. A redox secondary battery , wherein an electrolytic solution containing sulfuric acid of 6 M or more is used as an electrolytic solution for dissolving each vanadium ion of both active materials.
ションしない範囲内で使用する特許請求の範囲第１項記
載のレドックス型二次電池。2. The redox secondary battery according to claim 1, wherein the redox type secondary battery is used within a range in which the sulfuric acid concentration is not intercalated to the carbon electrode.
ムを晶析或は溶解させて使用する特許請求の範囲第２項
記載のレドックス型二次電池。3. The redox type secondary battery according to claim 2, which is used by controlling the liquid temperature of the electrolytic solution to crystallize or dissolve vanadium in the liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3074808A JPH07101615B2 (en) | 1991-03-14 | 1991-03-14 | Redox type secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3074808A JPH07101615B2 (en) | 1991-03-14 | 1991-03-14 | Redox type secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04286871A JPH04286871A (en) | 1992-10-12 |
| JPH07101615B2 true JPH07101615B2 (en) | 1995-11-01 |
Family
ID=13557980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3074808A Expired - Lifetime JPH07101615B2 (en) | 1991-03-14 | 1991-03-14 | Redox type secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07101615B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101436758B1 (en) * | 2013-12-23 | 2014-09-01 | 오씨아이 주식회사 | Vanadium redox flow battery |
| KR102395316B1 (en) | 2021-05-03 | 2022-05-04 | 주동식 | Adhesive tape manufacturing method with excellent adhesion |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4646358B2 (en) * | 1999-06-09 | 2011-03-09 | 関西電力株式会社 | Method for producing trivalent vanadium sulfate and method for producing vanadium electrolyte |
| JP4593732B2 (en) | 2000-07-04 | 2010-12-08 | 関西電力株式会社 | Method for producing trivalent and tetravalent mixed vanadium compound and method for producing vanadium electrolyte |
| JP3959234B2 (en) | 2000-12-26 | 2007-08-15 | 日本化学工業株式会社 | Modified vanadium compound, method for producing the same, electrolytic solution composition for redox flow type battery, and method for producing electrolytic solution for redox flow type battery |
| WO2014184617A1 (en) * | 2013-05-16 | 2014-11-20 | Hydraredox Technologies Holdings Ltd. | Estimation of the state of charge of a positive electrolyte solution of a working redox flow battery cell without using any reference electrode |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2724817B2 (en) * | 1986-02-11 | 1998-03-09 | ユニサーチ・リミテッド | All Vanadium Redox Battery |
| JPS6460967A (en) * | 1987-08-31 | 1989-03-08 | Sumitomo Electric Industries | Electrolyte for redox flow battery |
-
1991
- 1991-03-14 JP JP3074808A patent/JPH07101615B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101436758B1 (en) * | 2013-12-23 | 2014-09-01 | 오씨아이 주식회사 | Vanadium redox flow battery |
| KR102395316B1 (en) | 2021-05-03 | 2022-05-04 | 주동식 | Adhesive tape manufacturing method with excellent adhesion |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04286871A (en) | 1992-10-12 |
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