JPH0131672B2 - - Google Patents
Info
- Publication number
- JPH0131672B2 JPH0131672B2 JP57137357A JP13735782A JPH0131672B2 JP H0131672 B2 JPH0131672 B2 JP H0131672B2 JP 57137357 A JP57137357 A JP 57137357A JP 13735782 A JP13735782 A JP 13735782A JP H0131672 B2 JPH0131672 B2 JP H0131672B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- mol
- electrode
- secondary battery
- added
- 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
Links
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229940102001 zinc bromide Drugs 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims 1
- 210000001787 dendrite Anatomy 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/365—Zinc-halogen accumulators
-
- 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】
本発明は、亜鉛（Zn）−ハロゲン（例えばBr）
電解液循環型二次電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides zinc (Zn)-halogen (e.g. Br)
This invention relates to an electrolyte circulation type secondary battery.
第１図は、この亜鉛−ハロゲン電解液循環型二
次電池の基本構成図である。この電池は、単セル
１を隔膜（セパレータ）２によつて仕切つて、そ
の両側に陽極室３と陰極室４とを形成し、陽極室
３内に陽極（臭素電極）５を配置し、陰極室４内
に陰極（亜鉛電極）６を配置して構成されてい
る。陽極室３内には、陽極液貯蔵槽７から陽極液
（ZnBr2＋Br2）がポンプ９によつて循環し、ま
た、陰極室４には、陰極液貯蔵槽８から（例えば
ZnBr2）がポンプ１０によつて循環している。な
お１１，１２はバルブで、充放電時に開かれる。 FIG. 1 is a basic configuration diagram of this zinc-halogen electrolyte circulation type secondary battery. In this battery, a single cell 1 is partitioned by a diaphragm (separator) 2, an anode chamber 3 and a cathode chamber 4 are formed on both sides of the cell, an anode (bromine electrode) 5 is arranged inside the anode chamber 3, and a cathode A cathode (zinc electrode) 6 is disposed within a chamber 4. In the anode chamber 3, anolyte (ZnBr 2 +Br 2 ) is circulated from the anolyte storage tank 7 by a pump 9, and in the cathode chamber 4, from the catholyte storage tank 8 (e.g.
ZnBr 2 ) is circulated by a pump 10 . Note that 11 and 12 are valves that are opened during charging and discharging.
このような亜鉛電極を有する二次電池において
は、充電時種々の原因により陰極側に亜鉛が樹枝
状結晶（デンドライト）１３を以つて析出、生成
する。これは、次第に生長し、第２図に示すよう
に隔膜２を破り、対極（臭素極、塩素極）と短絡
したり、電極表面から脱落し、充放電時の電流密
度分布を不均一とし、電池のエネルギー効率を低
下させるとともに、電池寿命を短かくさせる原因
となつている。 In a secondary battery having such a zinc electrode, zinc precipitates and forms dendrites 13 on the cathode side due to various reasons during charging. This gradually grows, breaks the diaphragm 2 as shown in Figure 2, causes a short circuit with the counter electrode (bromine electrode, chlorine electrode), or falls off the electrode surface, making the current density distribution uneven during charging and discharging. This causes a decrease in battery energy efficiency and shortens battery life.
ここにおいて、本発明は、樹枝状結晶の析出を
効果的に抑制することのできる電解液を有する亜
鉛−ハロゲン二次電池を提供しようとするもので
ある。 Here, the present invention aims to provide a zinc-halogen secondary battery having an electrolytic solution that can effectively suppress precipitation of dendrites.
本発明に係る電池は、充放電に際しエネルギ効
率の急低下しない0.8〜3.0mol／の液組成をな
す電解液（塩化亜鉛液、臭化亜鉛液）に、２〜
3mol／の塩化カリウム（KCl）又は、２〜
4mol／の塩化アンモニウム（NH4Cl）を添加
した点に特徴がある。 In the battery according to the present invention, an electrolytic solution (zinc chloride solution, zinc bromide solution) having a liquid composition of 0.8 to 3.0 mol/min that does not cause a sudden drop in energy efficiency during charging and discharging.
3mol/potassium chloride (KCl) or 2~
It is characterized by the addition of 4 mol/ammonium chloride (NH 4 Cl).
第３図には、亜鉛を均一に電着させるために、
臭化亜鉛液（ZnBr2）1mol／にKCl、NH4Clを
０〜5mol／添加し、亜鉛デンドライト１３の
電極面からの高さｈ（第４図参照）を調べた実験
結果を示すものである。なお、ここで液PHは０〜
４、液温は−10℃〜60℃の範囲とする。 In Figure 3, in order to uniformly electrodeposit zinc,
This shows the results of an experiment in which 0 to 5 mol of KCl and NH 4 Cl were added to 1 mol of zinc bromide solution (ZnBr 2 ), and the height h from the electrode surface of zinc dendrite 13 (see Figure 4) was investigated. be. Note that the liquid pH here is 0~
4. The liquid temperature should be in the range of -10℃ to 60℃.
この実験結果から、KCl、NH4Clとも添加量を
増加させるほど、電極表面での亜鉛デンドライト
の析出量が減少し、特に、2mol／以上の添加
量で、均一電着性が増すことが認められる。すな
わち、デンドライト状析出亜鉛の高さは、KCI、
NH4Cl添加量が増えるに従つて、減少し、平滑
性が増している。KCl量は、1mol／ZnBr2中に
は3mol／まで、また、NH4Cl量は4mol／の
添加で、各々これ以上の添加量になると亜鉛折出
時に水素を発泡しやすくなり、これが限界溶解量
である。 From the results of this experiment, it was found that as the amount of both KCl and NH 4 Cl added increases, the amount of zinc dendrite precipitated on the electrode surface decreases, and in particular, when the amount added is 2 mol/or more, the uniform electrodeposition property increases. It will be done. That is, the height of dendrite-like precipitated zinc is KCI,
As the amount of NH 4 Cl added increases, it decreases and smoothness increases. The amount of KCl added is 1 mol/up to 3 mol/into ZnBr 2 , and the amount of NH 4 Cl is added up to 4 mol/into ZnBr 2.If the amount of each added is larger than this, hydrogen tends to bubble when zinc is precipitated, and this is the limit solubility. It is quantity.
以上の結果から、KClの最適添加量は２〜
3mol／、NH4Clの最適添加量は、２〜4mol／
である。なお、PHに関しては、０以下では激し
い水素発泡が生じ、また、４以上では亜鉛析出時
に水酸化亜鉛が析出しやすくなり、不均一電着性
を増加させている。したがつて、PHは０〜４が望
ましい。 From the above results, the optimal amount of KCl added is 2~
3 mol/, the optimum amount of NH 4 Cl added is 2 to 4 mol/
It is. Regarding pH, if it is less than 0, severe hydrogen foaming occurs, and if it is more than 4, zinc hydroxide tends to be deposited during zinc deposition, increasing non-uniform electrodeposition. Therefore, the pH is preferably 0 to 4.
実施例によれば、臭化亜鉛3mol／水溶液に
KCl2mol／を添加し、電極面積400cm2の炭素−
プラスチツク電極面に、PH２、室温にて電流密度
60mA／cm2で４時間充放電を行なつたところ、電
極全面にデンドライト皆無の均一な亜鉛電着が得
られた。 According to the example, 3 mol of zinc bromide/aqueous solution
Add KCl2mol/, carbon-
Current density on the plastic electrode surface at PH2 and room temperature
After charging and discharging at 60 mA/cm 2 for 4 hours, uniform zinc electrodeposition with no dendrites was obtained over the entire surface of the electrode.
以上説明したように、本発明によれば、樹枝状
結晶の析出を効果的に抑制することができるもの
で、電池のエネルギー効率の低下をなくし、長寿
命の亜鉛−ハロゲン二次電池を実現できる。 As explained above, according to the present invention, it is possible to effectively suppress the precipitation of dendrites, thereby eliminating a decrease in battery energy efficiency and realizing a long-life zinc-halogen secondary battery. .
第１図は亜鉛−ハロゲン二次電池の基本構成
図、第２図は樹枝状結晶析出の様子を示す説明
図、第３図は実験結果の一例を示す線図、第４図
は第３図の説明図である。
１……単セル、２……セパレータ、５，６……
電極、１３……デンドライト。
Figure 1 is a basic configuration diagram of a zinc-halogen secondary battery, Figure 2 is an explanatory diagram showing the state of dendrite precipitation, Figure 3 is a diagram showing an example of experimental results, and Figure 4 is Figure 3. FIG. 1... Single cell, 2... Separator, 5, 6...
Electrode, 13... dendrite.
Claims (1)
次電池において、 前記電解液として0.8〜3.0mol／の液組成を
なす塩化亜鉛液又は臭化亜鉛液を使用し、これに
２〜3mol／の塩化カリウム又は２〜4mol／
の塩化アンモニウムを添加したことを特徴とする
亜鉛−ハロゲン二次電池。[Scope of Claims] 1. In a secondary battery including a zinc electrode, a halogen electrode, and an electrolytic solution, a zinc chloride solution or a zinc bromide solution having a liquid composition of 0.8 to 3.0 mol/mole is used as the electrolytic solution; 2-3 mol/potassium chloride or 2-4 mol/
A zinc-halogen secondary battery characterized by adding ammonium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57137357A JPS5927479A (en) | 1982-08-09 | 1982-08-09 | Zinc-halogen secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57137357A JPS5927479A (en) | 1982-08-09 | 1982-08-09 | Zinc-halogen secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5927479A JPS5927479A (en) | 1984-02-13 |
| JPH0131672B2 true JPH0131672B2 (en) | 1989-06-27 |
Family
ID=15196762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57137357A Granted JPS5927479A (en) | 1982-08-09 | 1982-08-09 | Zinc-halogen secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5927479A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6412473A (en) * | 1987-07-03 | 1989-01-17 | Toyota Motor Corp | Zinc-bromine battery |
| JPS6459783A (en) * | 1987-08-28 | 1989-03-07 | Meidensha Electric Mfg Co Ltd | Battery operating method |
| WO2022102024A1 (en) * | 2020-11-11 | 2022-05-19 | 日本電信電話株式会社 | Iron zinc battery |
-
1982
- 1982-08-09 JP JP57137357A patent/JPS5927479A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5927479A (en) | 1984-02-13 |
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