JPS62170175A - Halogen active material secondary battery - Google Patents
Halogen active material secondary batteryInfo
- Publication number
- JPS62170175A JPS62170175A JP61010915A JP1091586A JPS62170175A JP S62170175 A JPS62170175 A JP S62170175A JP 61010915 A JP61010915 A JP 61010915A JP 1091586 A JP1091586 A JP 1091586A JP S62170175 A JPS62170175 A JP S62170175A
- Authority
- JP
- Japan
- Prior art keywords
- halogen
- gas
- carrier gas
- solvent
- pump
- 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.)
- Granted
Links
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 36
- 150000002367 halogens Chemical class 0.000 title claims abstract description 36
- 239000011149 active material Substances 0.000 title description 2
- 239000012159 carrier gas Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 abstract description 19
- 239000003792 electrolyte Substances 0.000 abstract description 16
- 229910052734 helium Inorganic materials 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachloro-1,3-butadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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)
- Fuel Cell (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は塩素、臭素等のハロゲンを正極活物質とした二
次電池においてハロゲンを必要に応じて供給可能とした
二次電池に関するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a secondary battery that uses halogen such as chlorine or bromine as a positive electrode active material, in which halogen can be supplied as needed. .
正極活物質にハロゲンを使用する電池において充電の際
生成するハロゲンを低温に保持した溶媒に吸収させ、放
電時には溶媒の温度を上昇させてハロゲンを放出させる
方法については既に提案されている。しかし放電時にハ
ロゲンを放出させる具体的な方法としては単に溶媒の温
度を上昇させることのみであった。実際の電池において
は、出力の変動に応じて活物質の供給速度を！１節する
必要があるが、その供給を単に温度上昇の手段によって
いたのでは必ずしも必要量のハロゲンを自由に供給する
ことができない、ハロゲンの放出は温度上昇によって、
単純比例的に起こるものではないからである。A method has already been proposed in which, in batteries that use halogen as the positive electrode active material, the halogen generated during charging is absorbed into a solvent kept at a low temperature, and the temperature of the solvent is raised during discharge to release the halogen. However, the only concrete method for releasing halogen during discharge was simply increasing the temperature of the solvent. In an actual battery, the supply rate of active material should be adjusted according to fluctuations in output! It is necessary to explain this in Section 1, but it is not necessarily possible to freely supply the necessary amount of halogen if the supply is simply by means of increasing the temperature.The release of halogen is caused by increasing the temperature.
This is because it does not occur in a simple proportional manner.
本発明の目的は上記ハロゲンを溶媒に吸収して貯蔵する
二次電池において放電時にハロゲンを必要に応じた速度
で自由に放出させることができる二次電池を開発するこ
とにある。An object of the present invention is to develop a secondary battery that stores the above-mentioned halogen by absorbing it in a solvent, and can freely release the halogen at a rate as required during discharge.
本発明はこのような目的を達成するため鋭意研究の結果
開発されたもので正極活物質にハロゲンを用いハロゲン
を溶媒に溶解して貯蔵する二次電池においてキャリアガ
スを系内に循環させておくことを特徴とする特
キャリアガスとしては通常Ｈｅ 、 Ａ ｒ 、 Ｎ
２等の不活性ガスが用いられる。The present invention was developed as a result of intensive research in order to achieve such an objective.In a secondary battery that uses halogen as a positive electrode active material and stores the halogen dissolved in a solvent, a carrier gas is circulated within the system. Special carrier gases characterized by this are usually He, Ar, and N.
An inert gas such as No. 2 is used.
電池系内にキャリアガスを循環させてその量及び径路を
調節することにより、必要に応じた量のハロゲンを供給
することができる。By circulating the carrier gas within the battery system and adjusting its amount and path, it is possible to supply the amount of halogen as needed.
以下図によって本発明の詳細な説明する。The present invention will be explained in detail below with reference to the drawings.
図は本発明二次電池の構成を示すもので電池全体は電池
部（１）、電解液槽（２）、吸収槽（３）からなってお
り図中実線で示した配管がガス循環系であり破線で示し
た配管が液循環系である。各線上の矢印は循環方向を示
す。The figure shows the configuration of the secondary battery of the present invention. The entire battery consists of a battery part (1), an electrolyte tank (2), and an absorption tank (3). The piping indicated by solid lines in the figure is the gas circulation system. The piping shown with dotted lines is the liquid circulation system. Arrows on each line indicate the direction of circulation.
電解液は液ポンプ（５）により電池部（１）と電解液槽
（２）の間を循環している。ハロゲンガスは充電時は電
池部より生成するがガスポンプ（４）により、電池部（
１）、吸収槽（３）電解液槽（２）の間を循環しており
、吸収槽（３）にて吸収される０本発明においては、こ
のガス循環系に一定量のＨｅ、Ａｒ等の不活性ガスをキ
ャリアガスとして循環させておくものでありこのことに
よりハロゲンはキャリアガスの流れに乗って運ばれハロ
ゲンの量が大巾に変動しても系全体のガスの流れは常に
確保され制御され易い。The electrolyte is circulated between the battery section (1) and the electrolyte tank (2) by a liquid pump (5). Halogen gas is generated from the battery part during charging, but the gas pump (4) generates halogen gas from the battery part (
1), absorption tank (3), and electrolyte tank (2), and is absorbed in the absorption tank (3).In the present invention, a certain amount of He, Ar, etc. is added to this gas circulation system. This system circulates an inert gas as a carrier gas, and as a result, the halogen is carried along with the flow of the carrier gas, and even if the amount of halogen fluctuates widely, the gas flow throughout the system is always ensured. Easy to control.
また、吸収槽中の溶媒は低温でハロゲンを吸収させた後
低速で温度を上昇させて行っても電解液中にガスを吹き
込まない限り過飽和状態を維持してハロゲンを放出しな
い性質を有するため、充電後吸収槽中に充分吸収させた
状態で保持しておきたい場合には従来の水和物にして貯
蔵する場合と違って特に冷却しなくても安全にハロゲン
を溶媒中に溶解保存出来る。この間はバルブ（６）を閉
じてバルブ（７）を開は貯蔵槽の気相部にキャリアガス
を素通りさせておけばよい、かくして保存されているハ
ロゲンを溶媒中より取り出すにはバルブ（７）を閉めて
バルブ（６）を開きキャリアガスを溶媒中に流しキャリ
アガスに乗せて外に取り出せばよい。In addition, the solvent in the absorption tank has the property of maintaining a supersaturated state and not releasing halogen unless gas is blown into the electrolyte, even if the temperature is raised slowly after absorbing halogen at a low temperature. If it is desired to maintain the halogen in a sufficiently absorbed state in the absorption tank after charging, the halogen can be safely dissolved and stored in a solvent without any particular cooling, unlike the conventional case of storing the halogen in the form of a hydrate. During this time, it is sufficient to close the valve (6) and open the valve (7) to allow the carrier gas to pass through the gas phase of the storage tank.To take out the stored halogen from the solvent, open the valve (7). , and open the valve (6) to allow the carrier gas to flow into the solvent and take it out on top of the carrier gas.
ハロゲン発生量は溶媒の温度によっても変化するがガス
ポンプ（４）の流量を調節することによって自由に変え
ることが出来る。The amount of halogen generated varies depending on the temperature of the solvent, but can be freely changed by adjusting the flow rate of the gas pump (4).
以上述べたように系内に絶えずキャリアガスをポンプに
て循環させかつバルブ（６）（７）の開閉により溶媒に
吸収されたハロゲンを希望する流量で発生させることが
できる。As described above, the halogen absorbed in the solvent can be generated at a desired flow rate by constantly circulating the carrier gas in the system using the pump and opening and closing the valves (6) and (7).
図に概略図を示したシステムを持つ二次電池を製作した
。We manufactured a secondary battery with the system shown schematically in the figure.
電池部：負極活物質には亜鉛を用い電極には宥効面積１
１００ｃｒｎ’の緻密グラファイトを用いた。Battery part: Zinc is used as the negative electrode active material, and the electrode has an effective area of 1
100 crn' dense graphite was used.
正極活物質には塩素を用い電極には有効面１１１００ｃ
ｒｎ’の多孔質グラファイトを用いた。Chlorine is used as the positive electrode active material, and the effective surface of the electrode is 11100c.
rn' porous graphite was used.
この正極、負極を用いて単セルを構成しこれを１５セル
直列、更に２並列として合計３０セルを用いてｔ ｏ
ｏ ｏｗの電池を構成した。A single cell is constructed using these positive and negative electrodes, and 15 cells are connected in series and 2 are connected in parallel for a total of 30 cells.
o ow battery was constructed.
電解液槽：２００１の貯槽に塩化亜鉛２モル、支持塩２
モルを溶解した水溶液を１００１入れて用いた。Electrolyte tank: 2 mol of zinc chloride, 2 supporting salts in the 2001 storage tank
An aqueous solution containing 1,001 moles of the solution was used.
塩素ガス吸収槽：１００ＪＬの貯槽にヘキサクロルブタ
ジェン６０文を満して用いた。Chlorine gas absorption tank: A 100 JL storage tank was filled with 60 g of hexachlorbutadiene.
以上の図のようにポンプ、バルブ、吹込管を用いて接続
し６０１／ｍｉｎの流速で電解液を電極と電解槽の間を
循環させｉｔｏｏｗで８時間充電した。この間気相には
キャリヤーガスとしてヘリウムを０．７ｋｇ／ｃｍ″Ｇ
入れて循環しバルブ（６）を開け、（７）を閉めて一５
℃に冷却したヘキサクロルブタジェンに発生する塩素ガ
スを吸収させた。充電後、バルブ（６）を閉じ、バルブ
（７）を開けてヘリウムの循環は続は加熱冷却装置（８
）により吸収槽の温度を２５℃迄上昇させた。この間吸
収槽の圧力は（９）のＰＩにして観察したがほぼ１ｋｇ
／ｃｒｎ’Ｇを示していた。その後（７）を閉め（６）
を開はポンプ（４）の速度を調整してキャリヤーガスの
流速を変えて取り出す塩素量を調整しながら循環を続は
電解液中の塩素濃度がＩｇ／見になるようにし、電解液
を電池と電解液槽の間で循環した。かくに１１０００ｋ
で７．５時間の放電を続けることが出来制御は非常に順
調に行なうことが出来た。As shown in the figure above, the electrolyte was connected using a pump, a valve, and a blowing pipe, and the electrolytic solution was circulated between the electrode and the electrolytic cell at a flow rate of 601/min, and the battery was charged with an itoo for 8 hours. During this period, helium was added as a carrier gas to the gas phase at a rate of 0.7 kg/cm''G.
Put it in, circulate it, open valve (6), close (7) and turn on
The generated chlorine gas was absorbed into hexachlorobutadiene cooled to ℃. After charging, close the valve (6) and open the valve (7) to continue the helium circulation.
) to raise the temperature of the absorption tank to 25°C. During this period, the pressure in the absorption tank was observed using PI (9), and it was approximately 1 kg.
/crn'G was shown. Then close (7) (6)
To open the pump, adjust the speed of the pump (4) and change the flow rate of the carrier gas to adjust the amount of chlorine taken out while circulating.Continue to circulate the electrolyte so that the chlorine concentration in the electrolyte is Ig/min. and the electrolyte tank. Kuni 11000k
We were able to continue discharging for 7.5 hours, and the control was very smooth.
以上述べた如く本発明二次電池においてはガス系に常に
キャリアガスを循環させてその一部を溶媒中に経由させ
ることにより系内のハロゲン濃度の制御を容易に行うこ
とができ、工業上顕著な効果を有するものである。As described above, in the secondary battery of the present invention, the halogen concentration in the system can be easily controlled by constantly circulating the carrier gas in the gas system and passing a part of it into the solvent, which is industrially remarkable. It has a great effect.
図は本発明二次電池の構成を示す概略図（１）電池部
（６）ガス系バルブ（２）電解液貯槽 （７）
ガス系バルブ（３）ハロゲン吸収槽（８）吸収槽加熱冷
却装置（４）ガス循環ポンプ（９）圧力指示計（５）電
解液循環ポンプ（１０）水素除去設備□ ガス循環系
一一一一 電解液循環系The figure is a schematic diagram showing the configuration of the secondary battery of the present invention (1) Battery section
(6) Gas system valve (2) Electrolyte storage tank (7)
Gas system valve (3) Halogen absorption tank (8) Absorption tank heating and cooling device (4) Gas circulation pump (9) Pressure indicator (5) Electrolyte circulation pump (10) Hydrogen removal equipment □ Gas circulation system 1111 Electrolyte circulation system
Claims (1)
貯蔵する二次電池において、キャリアガスを系内に循環
させておくことを特徴とするハロゲンを活物質とした二
次電池。A secondary battery using halogen as a positive electrode active material and storing the halogen dissolved in a solvent, characterized in that a carrier gas is circulated within the system.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61010915A JPS62170175A (en) | 1986-01-21 | 1986-01-21 | Halogen active material secondary battery |
| GB08614695A GB2177251B (en) | 1985-06-19 | 1986-06-17 | Battery |
| US06/875,868 US4728587A (en) | 1985-06-19 | 1986-06-18 | Battery using halogen as active material |
| FR8608844A FR2583926B1 (en) | 1985-06-19 | 1986-06-19 | ELECTROCHEMICAL GENERATOR, ESPECIALLY A BATTERY OR ACCUMULATOR, COMPRISING A HALOGEN AS AN ACTIVE INGREDIENT AND METHOD FOR OPERATING THE SAME |
| DE19863620556 DE3620556A1 (en) | 1985-06-19 | 1986-06-19 | BATTERY USING HALOGEN AS ACTIVE MATERIAL |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61010915A JPS62170175A (en) | 1986-01-21 | 1986-01-21 | Halogen active material secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62170175A true JPS62170175A (en) | 1987-07-27 |
| JPH0413833B2 JPH0413833B2 (en) | 1992-03-10 |
Family
ID=11763555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61010915A Granted JPS62170175A (en) | 1985-06-19 | 1986-01-21 | Halogen active material secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62170175A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003021709A1 (en) * | 2001-09-03 | 2003-03-13 | Andrey Veniaminovich Popov | Accumulator |
-
1986
- 1986-01-21 JP JP61010915A patent/JPS62170175A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003021709A1 (en) * | 2001-09-03 | 2003-03-13 | Andrey Veniaminovich Popov | Accumulator |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0413833B2 (en) | 1992-03-10 |
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