JPH0626144B2 - Secondary battery device charging / discharging method - Google Patents
Secondary battery device charging / discharging methodInfo
- Publication number
- JPH0626144B2 JPH0626144B2 JP59083494A JP8349484A JPH0626144B2 JP H0626144 B2 JPH0626144 B2 JP H0626144B2 JP 59083494 A JP59083494 A JP 59083494A JP 8349484 A JP8349484 A JP 8349484A JP H0626144 B2 JPH0626144 B2 JP H0626144B2
- Authority
- JP
- Japan
- Prior art keywords
- active material
- electrode active
- negative electrode
- positive electrode
- 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
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
- H01M12/085—Zinc-halogen cells or batteries
-
- 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
- Y02E60/10—Energy storage using batteries
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
Description
【発明の詳細な説明】 （発明の利用分野） 本発明は二次電池装置の充放電方法に関し、さらに詳し
くは非常時など緊急時に、充電能力以上の出力を得るこ
とができる、レドックス・フロー型の二次電池装置の充
放電方法に関するものである。Description: FIELD OF THE INVENTION The present invention relates to a charging / discharging method for a secondary battery device, and more particularly to a redox flow type device capable of obtaining an output higher than its charging capacity in an emergency such as an emergency. The present invention relates to a charging / discharging method for a secondary battery device.
（発明の背景） 本発明の対象となる二次電池は、溶液流通型の電池本体
（電解セル）に活物質溶液を送液する構造のもので、二
次電池を稼動させない時は、溶液はタンク内に貯蔵され
る。一般にこの種の電池をレドックス・フロー型二次電
池という。ここで活物質溶液とは、塩素水、塩酸酸性塩
化第一鉄水溶液等の正極液または負極液をいい、これら
の両方が電池本体に送液される。一般にこのような電池
においては、電池本体（電解セル）内での自己放電はほ
とんど起こらない。それは、停止時には、溶液はほとん
どタンク等に戻され、電池本体内には溶液が貯蔵されて
いないためである。しかし、タンク内に貯蔵された溶液
自身で自己放電が起こる可能性は充分にあり、例えば、
塩素を正極活物質とする電池は、塩素水（塩素水和物）
をタンク内に低温貯蔵するが、この塩素の放散による正
極活物質濃度の低下が起こり得る。また、クロム（２
価）を負極活物質とする場合は、不純物の負極液内への
混入によってクロム２価のプロトン還元反応が起こり、
このため、クロム２価濃度が減少してしまうことがあ
る。以上のように、溶液を電池本体に流通せしめて充放
電を行う形の電池も放置すると徐々にではあるが、その
蓄電量が減少するのが通常である。このため、多量の活
物質溶液を貯蔵しておいても、これを長期間保存して、
非常時の緊急放電用とするには問題がある。(Background of the Invention) A secondary battery to which the present invention is applied has a structure in which an active material solution is fed to a solution-flowing battery body (electrolytic cell), and when the secondary battery is not operated, the solution is Stored in the tank. Generally, this type of battery is called a redox flow secondary battery. Here, the active material solution refers to a positive electrode liquid or a negative electrode liquid such as chlorine water or hydrochloric acid-acidic ferrous chloride aqueous solution, and both of them are sent to the battery body. Generally, in such a battery, self-discharge hardly occurs in the battery body (electrolytic cell). This is because the solution is almost returned to the tank or the like when stopped, and the solution is not stored in the battery body. However, there is a sufficient possibility that self-discharge will occur in the solution itself stored in the tank, for example,
Batteries that use chlorine as the positive electrode active material are chlorine water (chlorine hydrate).
Is stored in a tank at a low temperature, but the concentration of the positive electrode active material may decrease due to the emission of chlorine. Also, chromium (2
Value) as the negative electrode active material, mixing of impurities into the negative electrode liquid causes a divalent chrome proton reduction reaction,
Therefore, the divalent chromium concentration may decrease. As described above, it is usual that the amount of electricity stored in a battery in which the solution is circulated through the battery main body to be charged and discharged is gradually, but gradually reduced. Therefore, even if a large amount of active material solution is stored, it can be stored for a long time,
There is a problem for emergency discharge in an emergency.
（発明の目的） 本発明の目的は、上記従来技術の問題点に鑑み、非常時
等の緊急放電用に備え、必要に応じて余剰出力を得るこ
とができる二次電池装置の充放電方法を提供することに
ある。(Object of the Invention) In view of the above-mentioned problems of the prior art, an object of the present invention is to provide a charging / discharging method for a secondary battery device, which is provided for emergency discharge in an emergency or the like and can obtain a surplus output as needed. To provide.
（発明の概要） 本発明は、正極活物質溶液および負極活物質溶液をそれ
ぞれ正極液ラインおよび負極液ラインを経て溶液流通型
電解槽に流通して電力を取り出す二次電池装置の充放電
方法において、放電時に、前記正極液ラインおよび／ま
たは負極液ラインへ系外から正極活物質および／または
負極活物質を導入することを特徴とする二次電池装置の
充放電方法である。(Summary of the Invention) The present invention relates to a charging / discharging method for a secondary battery device, in which a positive electrode active material solution and a negative electrode active material solution are respectively passed through a positive electrode liquid line and a negative electrode liquid line to a solution flow type electrolytic cell to take out electric power. In the charging / discharging method of the secondary battery device, a positive electrode active material and / or a negative electrode active material is introduced into the positive electrode liquid line and / or the negative electrode liquid line from outside the system during discharging.
本発明において、正、負両活物質を系外から導入するこ
とが好ましい。一方の活物質のみを導入しても放電容量
アップを図り得る場合は、電池の両活物質間に充電深度
のアンバランスが生じているときである。例えば、鉄−
クロム系レドックス・フロー型二次電池を用いる場合、
通常、正極活物質側が過充電になるので、容量アップは
３価のクロムを還元した２価のクロムを導入するのみで
も過充電分だけ容量アップを達成できる。In the present invention, it is preferable to introduce both positive and negative active materials from outside the system. The case where the discharge capacity can be increased by introducing only one of the active materials is when there is an imbalance in the charging depth between both active materials of the battery. For example, iron-
When using a chromium-based redox flow type secondary battery,
Usually, since the positive electrode active material side is overcharged, the capacity can be increased only by introducing divalent chromium, which is obtained by reducing trivalent chromium, by the amount of overcharge.
本発明によれば、反応によって充電状態の正極液または
負極液となる物質を貯蔵しておき、緊急放電時にこれら
の物質の反応を行わしめ、生成した活物質を正極または
負極液ラインに導入することによって、定格の充電量以
上の電力を得ることが好ましい。レドックス・フロー型
二次電池としては、クロム−鉄系、クロム−塩素系、鉄
−塩素系、バナジウム系、クロム−臭素系などが知られ
ており、次に述べるような方法で電極液ラインに導入す
る活物質が生成される。但し、例えばクロム−鉄系の電
池において、正極活物質は、先ず反応器で塩素を発生さ
せてそれを鉄２価を含む溶液（例えば正極液）中に放出
することによって正極活物質である鉄３価を作ることも
できる。According to the present invention, substances that become a positive electrode liquid or a negative electrode liquid in a charged state by the reaction are stored, the substances are reacted during an emergency discharge, and the generated active material is introduced into the positive electrode or negative electrode liquid line. Therefore, it is preferable to obtain electric power equal to or more than the rated charge amount. As the redox flow type secondary battery, chromium-iron system, chromium-chlorine system, iron-chlorine system, vanadium system, chromium-bromine system, etc. are known. The active material to be introduced is produced. However, for example, in a chromium-iron-based battery, the positive electrode active material is a positive electrode active material, which is produced by first generating chlorine in a reactor and releasing it into a solution containing divalent iron (eg, positive electrode solution). You can also make trivalent.
本発明において、電極液ラインに導入される活物質の生
成反応としては、まず正極活物質側では、該活物質が塩
素のようなハロゲンの場合、亜ハロゲン酸塩、次亜ハロ
ゲン酸塩と塩酸等の酸との反応、正極活物質が鉄（３
価）の場合、鉄酸化物への酸添加による鉄（３価）の生
成反応などがあり、負極活物質側では、該負極活物質が
クロム（２価）の場合、亜鉛等の金属によるクロム（３
価）の還元、同じく負極活物質が鉄（２価）の場合、鉄
等の金属や還元剤の添加による鉄（３価）の還元などが
あげられる。以上の活物質生成反応に用いる物質は、い
ずれも安価で入手しやすく、かつ保存中は化学的にきわ
めて安定であるため、好ましいものである。上記活物質
生成反応に用いる装置としては、充填物、撹拌手段等の
接触手段を備えた反応装置であれば良く、公知の接触装
置を使用することができる。In the present invention, as a reaction for producing the active material introduced into the electrode liquid line, first, on the positive electrode active material side, when the active material is a halogen such as chlorine, a halous acid salt, a hypohalous acid salt and hydrochloric acid are used. Reaction with acids such as
Valence), there is a reaction of producing iron (trivalent) by adding an acid to iron oxide. On the negative electrode active material side, when the negative electrode active material is chromium (divalent), chromium due to a metal such as zinc is used. (3
In the same manner, when the negative electrode active material is iron (divalent), reduction of iron (trivalent) by adding a metal such as iron or a reducing agent can be mentioned. All of the above-mentioned substances used for the active material formation reaction are preferable because they are inexpensive, easily available, and chemically extremely stable during storage. As an apparatus used for the above-mentioned active material formation reaction, a reaction apparatus provided with a contact means such as a packing and a stirring means may be used, and a known contact apparatus can be used.
本発明においては、活物質の生成反応装置を付設した二
次電池装置を用いることが好ましく、鉄−ハロゲン電池
のように正、負極活物質を溶液とするものは、両方の活
物質の生成反応装置をそれぞれ設けたものが好適に使用
される。In the present invention, it is preferable to use a secondary battery device provided with an active material generation reaction device, and a positive and negative electrode active material such as an iron-halogen battery as a solution is a reaction product of both active materials. Those provided with respective devices are preferably used.
以下、実施例により本発明をさらに詳細に説明する。Hereinafter, the present invention will be described in more detail with reference to Examples.
（発明の実施例） 第１図は、本発明の一実施例に用いる二次電池装置の構
成を示す説明図である。この装置は、液透過型電極であ
る正極２および負極３と、これらの間に設けられた隔膜
４と、これらのユニット毎に設けられた復極仕切板（端
部に位置する場合は端子板）５と、前記正極２および負
極３へそれぞれ極液を供給するための、正極液タンク
６、送液ポンプ１３および正極液ライン１４、ならびに
負極液タンク７、送液ポンプ１２および負極液ライン１
５と、正極液ライン１４の電池本体１の入口側に設けら
れたハロゲン酸化物反応器８および酸滴下タンク９と、
前記負極液ライン１５の電池入口側に設けられた四方コ
ック１１および該四方コックを介してバイパス状に設け
られた鉄充填塔１０およびバイパスライン２０とから主
として構成される。(Embodiment of the Invention) FIG. 1 is an explanatory diagram showing a configuration of a secondary battery device used in an embodiment of the present invention. This apparatus includes a positive electrode 2 and a negative electrode 3 which are liquid-permeable electrodes, a diaphragm 4 provided between them, and a depolarizing partition plate provided for each of these units (a terminal plate when positioned at an end portion). ) 5, a positive electrode liquid tank 6, a liquid feed pump 13 and a positive electrode liquid line 14, and a negative electrode liquid tank 7, a liquid feed pump 12 and a negative electrode liquid line 1 for supplying a polar liquid to the positive electrode 2 and the negative electrode 3, respectively.
5, a halogen oxide reactor 8 and an acid dropping tank 9 provided on the inlet side of the battery body 1 of the positive electrode liquid line 14,
It is mainly composed of a four-way cock 11 provided on the battery inlet side of the negative electrode liquid line 15, and an iron packed tower 10 and a bypass line 20 provided in a bypass shape through the four-way cock.
上記構成の装置において、本発明方法を用いない通常の
充放電の場合は、鉄−塩素電池の場合、充電状態では２
価の鉄イオン（Ｆｅ2+）の水溶液と塩素水（Ｃｌ２）が
それぞれ負極液タンク７および正極液タンク６に蓄えら
れ、これらを二次電池本体（流通型電解槽）１に流す
と、負極３ではＦｅ2+が電子を１個失い３価のＦｅ3+、
正極２では塩素分子が電子２個を受け取って、塩素イオ
ンＣｌ−となる。正極２と負極３で授受された電子は、
例えば外部回路を通って仕事をし、電力を放出する。以
上は通常運転の場合であるが、もし緊急時など、定格の
充電量以上の電力を得た場合には、反応器８のハロゲン
酸化物（またはハロゲン酸塩）にタンク９から塩酸など
のハロゲン酸を添加してハロゲンを発生させ、これを正
極液ライン１４に注入し、正極活物質を増加させ、定格
充電量以上の電力を得ることができる。また、負極活物
質については、ライン２０から負極活物質液（塩酸酸性
塩化第１鉄水溶液）を鉄片の充填塔１０を通過させて高
濃度の負極液を得、これを電池本体１の負極３に供給す
ることにより、定格充電量以上の電力を得ることができ
る。In the device having the above-mentioned configuration, in the case of normal charging / discharging not using the method of the present invention, in the case of an iron-chlorine battery, 2 in the charged state.
An aqueous solution of valent iron ions (Fe 2+ ) and chlorine water (Cl 2 ) are stored in the negative electrode liquid tank 7 and the positive electrode liquid tank 6, respectively, and when these are flown into the secondary battery main body (flow type electrolytic cell) 1, In the negative electrode 3, Fe 2+ loses one electron and trivalent Fe 3+ ,
At the positive electrode 2, the chlorine molecule receives two electrons and becomes chlorine ion Cl − . The electrons transferred between the positive electrode 2 and the negative electrode 3 are
For example, it works through an external circuit and releases power. The above is the case of normal operation, but if an electric power more than the rated charge is obtained in an emergency or the like, the halogen oxide (or halogen acid salt) of the reactor 8 is supplied with halogen such as hydrochloric acid from the tank 9. Halogen is generated by adding an acid, and this is injected into the positive electrode liquid line 14 to increase the positive electrode active material, and electric power equal to or higher than the rated charge amount can be obtained. Regarding the negative electrode active material, the negative electrode active material liquid (hydrochloric acid acidic ferric chloride aqueous solution) is passed from the line 20 through the iron piece packed tower 10 to obtain a high concentration negative electrode liquid, which is used as the negative electrode 3 of the battery body 1. By supplying the electric power to the electric power source, the electric power more than the rated charge amount can be obtained.
次に実施例の具体的実施例を示す。Next, specific examples of the examples will be described.
実施例１ 第１図に示した装置を用い、正極側の反応器８のハロゲ
ン酸化物としてさらし粉（次亜塩素酸カルシウム）、タ
ンク９から滴下する酸として塩酸を用い、また負極側の
充填塔１０には鉄片を充填した反応塔を用い、鉄−塩素
電池１の充放電実験を行った。本発明方法を用いない場
合（鉄充填塔１０およびハロゲン酸化物反応器８を用い
ない場合）は、電池１の蓄電量は約５０Ａｈｒであり、
室温で運転して完全充電を行った後、約４０Ａｈｒ放電
させ、その時点で四方コック１１および酸滴下タンクの
バルブ９Ａを開いて活物質を生成し、これを正極液ライ
ン１４に導入したところ、さらに一定電力の放電を続行
した。その結果、全放電量は９０Ａｈｒに達した。Example 1 Using the apparatus shown in FIG. 1, bleaching powder (calcium hypochlorite) was used as the halogen oxide of the reactor 8 on the positive electrode side, hydrochloric acid was used as the acid dropped from the tank 9, and the packed column on the negative electrode side was used. As a reference numeral 10, a reaction tower filled with iron pieces was used, and a charge-discharge experiment of the iron-chlorine battery 1 was performed. When the method of the present invention is not used (when the iron packed column 10 and the halogen oxide reactor 8 are not used), the amount of electricity stored in the battery 1 is about 50 Ahr,
After operating at room temperature for complete charging, about 40 Ahr discharge was performed, at which point the four-way cock 11 and the valve 9A of the acid dropping tank were opened to generate an active material, which was introduced into the positive electrode liquid line 14, Further, the discharge of constant power was continued. As a result, the total discharge amount reached 90 Ahr.
（発明の効果） 以上、本発明によれば、レドックス・フロー型二次電池
システムに系外から活物質を導入することにより、通常
の二次電池システムの蓄電量を越えて緊急放電用として
の出力を得ることができる。本発明方法は、遠隔地など
で自然エネルギーを蓄電する場合には特に有用である。(Effects of the Invention) As described above, according to the present invention, by introducing an active material from outside the system into a redox flow type secondary battery system, the amount of electricity stored in a normal secondary battery system is exceeded, and the battery is used for emergency discharge. You can get the output. The method of the present invention is particularly useful when storing natural energy in a remote place.
第１図は、本発明の一実施例に用いる二次電池装置を示
す系統図である。 １……電池本体、２……正極、３……負極、４……隔
膜、５……端子板（または複極仕切板）、６……正極液
タンク、７……負極液タンク、８……ハロゲン酸化物反
応器、９……酸滴下タンク、１０……鉄充填塔、１４…
…正極液ライン、１５……負極液ライン。FIG. 1 is a system diagram showing a secondary battery device used in one embodiment of the present invention. 1 ... Battery main body, 2 ... Positive electrode, 3 ... Negative electrode, 4 ... Separation film, 5 ... Terminal plate (or bipolar plate partition plate), 6 ... Cathode liquid tank, 7 ... Anode liquid tank, 8 ... … Halogen oxide reactor, 9… Acid dropping tank, 10… Iron packed tower, 14…
… Cathode line, 15 …… Negative line.
Claims (4)
れぞれ正極液ラインおよび負極液ラインを経て溶液流通
型電解槽に流通して電力を取り出す二次電池装置の充放
電方法において、放電時に、前記正極液ラインおよび／
または負極液ラインへ系外から正極活物質および／また
は負極活物質を導入することを特徴とする二次電池装置
の充放電方法。1. A charging / discharging method for a secondary battery device, wherein a positive electrode active material solution and a negative electrode active material solution are circulated through a positive electrode liquid line and a negative electrode liquid line into a solution flow type electrolytic cell to take out electric power. The positive electrode line and /
Alternatively, a method of charging and discharging a secondary battery device, which comprises introducing a positive electrode active material and / or a negative electrode active material into the negative electrode liquid line from outside the system.
活物質および負極活物質の少なくとも一方は、ハロゲン
酸化物に酸を加えて生成したハロゲンであることを特徴
とする二次電池装置の充放電方法。2. The secondary battery device according to claim 1, wherein at least one of the positive electrode active material and the negative electrode active material is a halogen produced by adding an acid to a halogen oxide. Charge / discharge method.
活物質および負極活物質の少なくとも一方は、クロム３
価を亜鉛をはじめとする金属で還元した２価のクロムで
あることを特徴とする二次電池装置の充放電方法。3. The method according to claim 1, wherein at least one of the positive electrode active material and the negative electrode active material is chromium 3
A charging / discharging method for a secondary battery device, which is divalent chromium whose valence is reduced by a metal such as zinc.
活物質および負極活物質の少なくとも一方は、２価の鉄
イオンを酸化した３価の鉄イオンであることを特徴とす
る二次電池装置の充放電方法。4. The secondary battery according to claim 1, wherein at least one of the positive electrode active material and the negative electrode active material is trivalent iron ion obtained by oxidizing divalent iron ion. Device charging and discharging method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59083494A JPH0626144B2 (en) | 1984-04-25 | 1984-04-25 | Secondary battery device charging / discharging method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59083494A JPH0626144B2 (en) | 1984-04-25 | 1984-04-25 | Secondary battery device charging / discharging method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60227364A JPS60227364A (en) | 1985-11-12 |
| JPH0626144B2 true JPH0626144B2 (en) | 1994-04-06 |
Family
ID=13804031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59083494A Expired - Lifetime JPH0626144B2 (en) | 1984-04-25 | 1984-04-25 | Secondary battery device charging / discharging method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0626144B2 (en) |
-
1984
- 1984-04-25 JP JP59083494A patent/JPH0626144B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60227364A (en) | 1985-11-12 |
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