JPS62281278A - Flat shaped alkali zinc storage battery - Google Patents
Flat shaped alkali zinc storage batteryInfo
- Publication number
- JPS62281278A JPS62281278A JP61124462A JP12446286A JPS62281278A JP S62281278 A JPS62281278 A JP S62281278A JP 61124462 A JP61124462 A JP 61124462A JP 12446286 A JP12446286 A JP 12446286A JP S62281278 A JPS62281278 A JP S62281278A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- electrode
- zinc
- zinc electrode
- calcium hydroxide
- 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.)
- Pending
Links
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 61
- 239000011701 zinc Substances 0.000 title claims abstract description 61
- 239000003513 alkali Substances 0.000 title 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 24
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 14
- 210000001787 dendrite Anatomy 0.000 abstract description 13
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 239000011149 active material Substances 0.000 abstract description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000004080 punching Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- XGRYDJSRYGHYOO-UHFFFAOYSA-N Thesine Natural products C1=CC(O)=CC=C1C1C(C(=O)OCC2C3CCCN3CC2)C(C=2C=CC(O)=CC=2)C1C(=O)OCC1C2CCCN2CC1 XGRYDJSRYGHYOO-UHFFFAOYSA-N 0.000 abstract 1
- 239000008151 electrolyte solution Substances 0.000 abstract 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract 1
- 229940101209 mercuric oxide Drugs 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- -1 zincate ions Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 240000005528 Arctium lappa Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- 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
- H01M10/24—Alkaline 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
（イ） 産業上の利用分野
本発明は負極活物質に亜鉛を用いる扁平型アルカリ亜鉛
蓄電池に関する。Detailed Description of the Invention 3. Detailed Description of the Invention (a) Field of Industrial Application The present invention relates to a flat alkaline zinc storage battery using zinc as a negative electrode active material.
（ロ）従来の技術
アルカリ亜鉛蓄電池の負極として用いられる亜鉛極では
、放電時に活物質である亜鉛がアルカリ電解液に溶出し
て亜鉛酸イオンとなり、充電時に亜鉛極表面に亜鉛とな
って析出する反応が起こる。この反応は特にエツジ効果
などにより電流が集中し易い亜鉛極間辺部に起こり易く
、亜鉛極周辺部では亜鉛の析出の際にデンドライトが生
長し、充放電サイクルが経過して行くと、前記デンドラ
イトがセパレータを貫通して対極に到達して内部短絡を
起こすため、電池のサイクル寿命が短くなるという問題
点があった。(b) Conventional technology In the zinc electrode used as the negative electrode of an alkaline zinc storage battery, the active material zinc is eluted into the alkaline electrolyte during discharge and becomes zincate ions, which are deposited as zinc on the surface of the zinc electrode during charging. A reaction occurs. This reaction is particularly likely to occur in the area between the zinc electrodes where current tends to concentrate due to the edge effect, etc. In the area around the zinc electrode, dendrites grow during the precipitation of zinc, and as the charge/discharge cycle progresses, the dendrites grow. Penetrates through the separator and reaches the counter electrode, causing an internal short circuit, resulting in a shortened cycle life of the battery.
このような問題を解決するために特開昭５７−７０６３
号公報では亜鉛極の表面を水酸化カルシウムで被覆する
ことが提案きれ、また特公昭５６−１９７０９号公報で
は亜鉛極の周辺部に水酸化カルシウム層を形成すること
が提案されており、何れも亜鉛極から溶出する亜鉛酸イ
オンを水酸化カルシウムによって亜鉛酸カルシウムの形
で固定してデンドライトの生長を抑制するようにしてい
る。In order to solve such problems, Japanese Patent Application Laid-Open No. 57-7063
In Japanese Patent Publication No. 1970-1970, it was proposed to coat the surface of the zinc electrode with calcium hydroxide, and in Japanese Patent Publication No. 56-19709, it was proposed to form a calcium hydroxide layer around the zinc electrode. The zincate ions eluted from the zinc electrode are fixed in the form of calcium zincate by calcium hydroxide to suppress the growth of dendrites.
ところが扁平型寛池では亜鉛極が直接あるいは集電体を
介して電池缶と接触しており、また亜鉛極の外側面と電
池缶の内周面の間には構造上電解液が遊離して溜まるの
で、亜鉛極周辺部に水酸化カルシウム層を配設しただけ
では充分ではなく、電解液が豊富に存在する亜鉛極外側
部からデンドライトが生長し、これが原因となってサイ
クル寿命が短くなっていた。However, in flat type Hiroike ponds, the zinc electrode is in contact with the battery can either directly or through a current collector, and due to the structure, electrolyte is loose between the outer surface of the zinc electrode and the inner circumferential surface of the battery can. Therefore, simply placing a calcium hydroxide layer around the zinc electrode is not sufficient, and dendrites grow from the outer part of the zinc electrode where electrolyte is abundant, which shortens the cycle life. Ta.
（ハ）発明が解決しようとする問題点
本発明は扁平型アルカリ亜鉛蓄電池における亜鉛極外側
部からのデンドライトの生長を抑制し、サイクル寿命を
向上させようとするものである。(c) Problems to be Solved by the Invention The present invention aims to suppress the growth of dendrites from the outer part of the zinc in a flat alkaline zinc storage battery, thereby improving the cycle life.
り二）問題点を解決するための手段
本発明の扁平型アルカリ亜鉛蓄電池は、亜鉛極を電池缶
の内底面に載置し、前記亜鉛極の外側面と電池缶の内側
面との間の空間に水酸化カルシウムを充填したものであ
る。2) Means for Solving the Problems The flat alkaline zinc storage battery of the present invention has a zinc electrode placed on the inner bottom surface of the battery can, and a gap between the outer surface of the zinc electrode and the inner surface of the battery can. The space is filled with calcium hydroxide.
（ホ）作用
亜鉛極の外側面と電池缶の内側面との間の空間に水酸化
力ルンウムを充填すると、亜鉛極の外側部に遊離した電
解液が溜ることが防止できデンドライト発生が防止でき
る。また扁平型電池のニッケル極と対向する亜鉛極外側
縁の盛り上り、溶出等による変形が防止できる。したが
って亜鉛極外側縁から生長せるデンドライトがセパレー
タと電池缶との間より延出して正極と短絡したり、また
亜鉛極変形によりセパレータをおし上げ正極と短絡しや
すくなる傾向を防止できうるものである。(e) Filling the space between the outer surface of the working zinc electrode and the inner surface of the battery can with hydroxide can prevent free electrolyte from accumulating on the outer surface of the zinc electrode, thereby preventing the formation of dendrites. . Further, deformation due to swelling, elution, etc. of the outer edge of the zinc electrode facing the nickel electrode of a flat battery can be prevented. Therefore, it is possible to prevent dendrites that grow from the outer edge of the zinc electrode from extending out from between the separator and the battery can and causing a short circuit with the positive electrode, and also to prevent deformation of the zinc electrode, which tends to push the separator down and cause a short circuit with the positive electrode. be.
また充填せる水酸化カルシウムはセパレータと画一
船橋と電池缶により囲まれた部分に存在仕ることができ
、従来、水酸化カルシウム配置時に必要ときれていた糊
料を必要とすることがなく、きわめて容易な充填工程と
なる。また′＠鉛船橋ｔ池缶に挿入後、水酸化カルシウ
ムを充填するので、亜鉛極に水酸化カルシウムを配置し
たものを電池缶に挿入するものに比べ、水酸化カルシウ
ムの脱落が少なく水酸化カルシウムの効果を十分に発揮
できる。In addition, the calcium hydroxide to be filled can be present in the area surrounded by the separator, uniform bridge, and battery can, and there is no need for glue, which was conventionally required when placing calcium hydroxide. This makes the filling process extremely easy. In addition, since calcium hydroxide is filled after the battery is inserted into the lead Funabashi T-ike can, less calcium hydroxide falls out than when calcium hydroxide is placed on the zinc electrode and inserted into the battery can. The effect can be fully demonstrated.
（へ）実施例
活物質として酸化亜鉛粉末１００重量部と金属亜鉛粉末
１０！量部、添加剤として酸化水銀５！量部、結着剤と
してフッ素樹脂ディスパージョン５重量部に水を加え混
練した後、ローラによりシート状にし、円形に打ち抜き
、乾燥移せたものを亜鉛極とした。そしてこの表面に水
酸化カルシウムを塗布し乾燥移せ、電池缶に挿入した。(f) Example active material: 100 parts by weight of zinc oxide powder and 10 parts by weight of metal zinc powder! Parts, mercury oxide as additive 5! After adding 5 parts by weight of water to 5 parts by weight of a fluororesin dispersion as a binder and kneading, the sheet was formed into a sheet using a roller, punched into a circular shape, and dried and transferred to form a zinc electrode. Calcium hydroxide was then applied to the surface, dried, and inserted into a battery can.
電池缶の内側面と亜鉛欄外側面との空間に水酸化カルシ
ウムを充填し、前記亜鉛極上にセパレータを介して、公
知の焼結式ニッケル極を円形に打ち抜いた正極を載置し
、所定の電解液量を注入後密閉し、本発明電池（Ａ）を
得た。The space between the inside surface of the battery can and the side surface of the zinc rail is filled with calcium hydroxide, and a positive electrode made by punching a known sintered nickel electrode into a circular shape is placed on top of the zinc electrode with a separator interposed therebetween, and a predetermined electrolysis process is carried out. After injecting the amount of liquid, the cell was sealed to obtain a battery (A) of the present invention.
韻
第１図は本発明電池（Ａ）の縦断面を表すものであり、
ニッケル極３がバネ２を介して正極缶１に接続されてお
り、亜鉛極９表面には水酸化カルシウム塗布層８′ｏが
あり、亜鉛極９外側面と電極缶４の内側面との間の空間
には８ａとして水酸化カルシウムが充填されている。こ
れら亜鉛極９とニッケル極３はセパレータ６、保液層７
を介して対向しており、正極缶１および電極缶４はバッ
キング５を介して密閉されている。尚、１０は絶縁リン
グであり電池缶からのデンドライト発生によるニッケル
極３との短絡を防止するものである。Figure 1 shows a longitudinal section of the battery (A) of the present invention.
The nickel electrode 3 is connected to the positive electrode can 1 via the spring 2, and there is a calcium hydroxide coating layer 8'o on the surface of the zinc electrode 9, and between the outer surface of the zinc electrode 9 and the inner surface of the electrode can 4. The space 8a is filled with calcium hydroxide. These zinc electrodes 9 and nickel electrodes 3 are connected to a separator 6 and a liquid retaining layer 7.
The positive electrode can 1 and the electrode can 4 are sealed with a backing 5 in between. Note that 10 is an insulating ring that prevents short circuit with the nickel electrode 3 due to dendrite generation from the battery can.
比較例１
負極に御坊水酸化カルシウムを含まないものを比較電池
（Ｂ）とした。Comparative Example 1 A comparative battery (B) did not contain Gobo calcium hydroxide in the negative electrode.
比較例２
負極の表面には水酸化カルシウムが塗布しであるが、電
池缶内側面と亜鉛極外側面との間の空間に水酸化カルシ
ウムが充填されていないものを比較電池（Ｃ）とした。Comparative Example 2 A comparative battery (C) was prepared in which the surface of the negative electrode was coated with calcium hydroxide, but the space between the inner surface of the battery can and the outer surface of the zinc electrode was not filled with calcium hydroxide. .
第２１ＸＩにおいて本発明電池（Ａ）と比較電池（Ｂ）
、（Ｃ）の充放電サイクルにおける放電容量を比較した
ものである。In the 21st XI, the invention battery (A) and the comparative battery (B)
, (C) are compared in terms of discharge capacity during charge/discharge cycles.
図より明らかなように電極缶内側面と亜鉛極外側との間
の空間に水酸化カルシウムを充填した本発明電池（Ａ）
はサイクル特性が非常に優れるものであることがわかる
。As is clear from the figure, the battery of the present invention (A) in which the space between the inner surface of the electrode can and the zinc outer side is filled with calcium hydroxide
It can be seen that the cycle characteristics are very excellent.
また比較電池（Ｂ）を上記テスト後分解したところ亜鉛
極の正極と対向する面にデンドライトが発生し、正極と
微小ショートしていた。比較１池（Ｃ）は電極端縁に電
池が集中するエツジ効果により亜鉛極周辺部の変形なら
びに亜鉛極外側面の端縁部からのデンドライト発生がみ
られた。これらの結果から考でするに、亜鉛極外側面と
電池缶内側面との空間部に水酸化カルシウムを充填する
ことにより、亜鉛極を外側周囲の亜鉛酸イオンが固定さ
れ、扁平型電池特有の亜鉛極外側面の端縁部からのデン
ドライト発生、亜鉛極周辺部の変形を本発明によれば扁
平型アルカリ亜鉛蓄電池の電池缶内側面と亜鉛極外側面
との間の空間に水酸化力ルンウムを充填することにより
、亜鉛極外側面の端縁部からデンドライトの発生ならび
に亜鉛極端縁部の変形を抑制することができ、サイクル
特性のきわめて優れた扁平型アルカリ亜鉛蓄電池が得ら
れる。Further, when the comparative battery (B) was disassembled after the above test, dendrites were generated on the surface of the zinc electrode facing the positive electrode, and a slight short circuit was caused with the positive electrode. Comparison 1 cell (C) showed deformation around the zinc electrode and generation of dendrites from the edge of the outer surface of the zinc electrode due to the edge effect in which cells were concentrated at the edge of the electrode. Based on these results, we believe that by filling the space between the outer surface of the zinc electrode and the inner surface of the battery can with calcium hydroxide, the zincate ions around the outer surface of the zinc electrode are fixed, which is unique to flat batteries. According to the present invention, generation of dendrites from the edge of the outer surface of the zinc electrode and deformation of the surrounding area of the zinc electrode can be prevented by the generation of hydroxide in the space between the inner surface of the battery can and the outer surface of the zinc electrode of a flat alkaline zinc storage battery. By filling the battery, it is possible to suppress the generation of dendrites from the edge of the zinc outer surface and the deformation of the zinc extreme edge, thereby obtaining a flat alkaline zinc storage battery with extremely excellent cycle characteristics.
第１図は本発明電池の縦断面図であり、第２図はサイク
ル特性図である。
（Ａ）・・・本発明電池、（Ｂ）、（Ｃ）・・・比較電
池１・・・正極缶、２・・・ばね、３・・・ニッケル極
、４・・・１１１８缶、５・・・バッキング、６・・・
セパレータ、７・・・保液層、８ａ・・・水酸化カルシ
ウム充填１．８ｂ・・・水酸化力ルンウム塗布層、９・
・・亜鉛極、１０・・・絶縁リング
ブイフル数FIG. 1 is a longitudinal sectional view of the battery of the present invention, and FIG. 2 is a cycle characteristic diagram. (A)...Battery of the present invention, (B), (C)...Comparative battery 1...Positive electrode can, 2...Spring, 3...Nickel electrode, 4...1118 can, 5 ...Backing, 6...
Separator, 7...liquid retaining layer, 8a...calcium hydroxide filling 1.8b...hydroxide coating layer, 9.
・・Zinc electrode, 10・・Number of insulation ring buoys
Claims (1)
電極体を電池缶に収納してなる扁平型電池において、前
記亜鉛極を電池缶の内底面に載置し前記亜鉛極の外側面
と電池缶の内側面との間の空間に水酸化カルシウムを充
填したことを特徴とする扁平型アルカリ亜鉛蓄電池。(1) In a flat battery in which an electrode body composed of a zinc electrode, a positive electrode, and a separator is housed in a battery can, the zinc electrode is placed on the inner bottom surface of the battery can, and the outer surface of the zinc electrode is placed on the inner bottom surface of the battery can. A flat alkaline zinc storage battery characterized by filling the space between the inside surface of the battery can and the inside surface of the battery can with calcium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61124462A JPS62281278A (en) | 1986-05-29 | 1986-05-29 | Flat shaped alkali zinc storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61124462A JPS62281278A (en) | 1986-05-29 | 1986-05-29 | Flat shaped alkali zinc storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62281278A true JPS62281278A (en) | 1987-12-07 |
Family
ID=14886120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61124462A Pending JPS62281278A (en) | 1986-05-29 | 1986-05-29 | Flat shaped alkali zinc storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62281278A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS519132A (en) * | 1974-07-15 | 1976-01-24 | Nippon Rubber Co | Hitofubutsuno hyomenniteikeino tofusoo keiseisuru hoho |
| JPS5619709A (en) * | 1979-07-27 | 1981-02-24 | Toma Kohan Kk | Aggregate column wood and its manufacture |
-
1986
- 1986-05-29 JP JP61124462A patent/JPS62281278A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS519132A (en) * | 1974-07-15 | 1976-01-24 | Nippon Rubber Co | Hitofubutsuno hyomenniteikeino tofusoo keiseisuru hoho |
| JPS5619709A (en) * | 1979-07-27 | 1981-02-24 | Toma Kohan Kk | Aggregate column wood and its manufacture |
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