JPS62243252A - Sealed alkaline manganese secondary battery - Google Patents
Sealed alkaline manganese secondary batteryInfo
- Publication number
- JPS62243252A JPS62243252A JP61085384A JP8538486A JPS62243252A JP S62243252 A JPS62243252 A JP S62243252A JP 61085384 A JP61085384 A JP 61085384A JP 8538486 A JP8538486 A JP 8538486A JP S62243252 A JPS62243252 A JP S62243252A
- Authority
- JP
- Japan
- Prior art keywords
- cadmium
- zinc
- alloy
- active material
- content
- 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 8
- 229910052748 manganese Inorganic materials 0.000 title claims description 8
- 239000011572 manganese Substances 0.000 title claims description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007773 negative electrode material Substances 0.000 claims abstract description 8
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 7
- 229910000925 Cd alloy Inorganic materials 0.000 claims abstract description 4
- 229910000645 Hg alloy Inorganic materials 0.000 claims abstract description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 7
- 238000005275 alloying Methods 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M10/34—Gastight accumulators
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、密閉型アルカリマンガン二次電池の改良に関
するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to improvements in sealed alkaline manganese secondary batteries.
従来の技術
従来まで、この種の密閉型二次電池で充放電サイクル特
性の向上については数多くの提案があるが、定電圧で長
時間充電された場合の耐圧特性向上については、負極活
物質である亜鉛に、酸化亜鉛を加えるなどのわずかな提
案しかなされていない０
発明が解決しようとする問題点
この種の二次電池は一般に耐圧試験中に、電解液の水分
解が生じ、正極より酸素ガスが、また負極より水素ガス
が発生する。そのために電池膨張が生じ、ひどい時には
電池の破裂を生じる。前述したように負極より発生する
水素ガスに対しては、負極に酸化亜鉛を混入させるなど
の方法によりかなシの改良がなされてきたが、それでも
不充分であり、正極から発生する酸素ガスによる電池膨
張もあり、現在まで広く実用化されるには至っていない
。Conventional Technology Until now, there have been many proposals for improving the charge-discharge cycle characteristics of this type of sealed secondary battery, but it has been proposed that negative electrode active materials be used to improve the voltage resistance characteristics when charged at a constant voltage for long periods of time. Only a few proposals have been made, such as adding zinc oxide to a certain type of zinc.0 Problems to be Solved by the Invention In this type of secondary battery, water decomposition occurs in the electrolyte during a pressure test, and oxygen is removed from the positive electrode. Hydrogen gas is also generated from the negative electrode. This causes the battery to expand and, in severe cases, cause the battery to explode. As mentioned above, improvements have been made to the hydrogen gas generated from the negative electrode by methods such as mixing zinc oxide into the negative electrode, but this is still insufficient, and batteries using oxygen gas generated from the positive electrode have been improved. Due to expansion, it has not been widely put into practical use until now.
本発明は、従来のガス発生による電池膨張、破裂といっ
た問題点を解決することによって、耐圧特性に優れた密
閉型アルカリマンガン二次電池を提供することを目的と
するものである。An object of the present invention is to provide a sealed alkaline manganese secondary battery with excellent pressure resistance by solving the conventional problems of battery expansion and rupture due to gas generation.
問題点を解決するだめの手段
この問題点を解決するために本発明は、負極活物質を亜
鉛と水銀とカドミウムの合金とし、かつカドミウム含有
量を、合金の５〜２０重量％としたものである。Means to Solve the Problem In order to solve this problem, the present invention uses an alloy of zinc, mercury, and cadmium as the negative electrode active material, and sets the cadmium content to 5 to 20% by weight of the alloy. be.
作用
この範囲の量のカドミウムを負極活物質である亜鉛と合
金化することにより、正極より発生する酸素ガスを亜鉛
合金に効率良く吸収させることができ、かつカドミウム
量がこの範囲であれば亜鉛の反応効率を劣化させること
もない。また、水銀は亜鉛の腐食防止のために一般によ
く用いられており、本発明においても数％が必要である
。元来、亜鉛も酸素ガスを吸収する能力は有しているが
、カドミウムはさらにその能力が高いため、この合金化
によって正極で発生する酸素ガスを、負極で効率良く吸
収することができ、電池膨張のない耐圧特性の優れた密
閉型アルカリマンガン二次電池を得ることができる。Effect By alloying cadmium in an amount within this range with zinc, which is an active material for the negative electrode, oxygen gas generated from the positive electrode can be efficiently absorbed into the zinc alloy. There is no deterioration in reaction efficiency. Further, mercury is generally often used to prevent corrosion of zinc, and in the present invention, several percent is required. Zinc originally has the ability to absorb oxygen gas, but cadmium has an even higher ability, so by alloying it, the oxygen gas generated at the positive electrode can be efficiently absorbed at the negative electrode. A sealed alkaline manganese secondary battery that does not expand and has excellent pressure resistance characteristics can be obtained.
実施例 以下図を用いて、本発明の一実施例を説明する。Example An embodiment of the present invention will be described below with reference to the drawings.
図は本発明のボタン型アルカリマンガン二次電池の断面
図である。本実施例では直径１１．６ｆｆ、高さ３．Ｏ
ｆｆの大きさの電池を用いた。The figure is a sectional view of a button-type alkaline manganese secondary battery of the present invention. In this example, the diameter is 11.6 ff and the height is 3. O
A battery of size ff was used.
図において、１は鉄にニッケルメッキした正極ケース、
２は主として二酸化マンガンよりなる正極、３は鉄にニ
ッケルメッキした正極リング、４はポリエチレンのグラ
フト重合膜よケなるセノくレータ、６はセルロースより
なる電解液含浸材、６はナイロンよりなる封口リング、
７は本発明のカドミウム含有率が１０重量％水銀含有量
９重量％の亜鉛粒子よりなる負極活物質、８はニッケル
ーステンレス鋼−銅の三層クラツド材よりなる負極端子
を兼ねる封口板である。In the figure, 1 is a positive electrode case made of nickel-plated iron;
2 is a positive electrode mainly made of manganese dioxide, 3 is a positive electrode ring made of nickel plated iron, 4 is a cenolator made of a polyethylene graft polymer film, 6 is an electrolyte-impregnated material made of cellulose, and 6 is a sealing ring made of nylon. ,
7 is a negative electrode active material of the present invention made of zinc particles having a cadmium content of 10% by weight and a mercury content of 9% by weight, and 8 is a sealing plate which also serves as a negative electrode terminal and is made of a three-layer cladding material of nickel-stainless steel-copper. .
このような本発明の実施例の電池と、従来の電池の比較
を以下に示す。なお試験は第１表に示すカドミウム量を
含む亜鉛合金の負極を用いた電池で行った。A comparison between the battery according to the embodiment of the present invention and a conventional battery will be shown below. The test was conducted using a battery using a zinc alloy negative electrode containing the amount of cadmium shown in Table 1.
第１表
ただし水銀は９重量％
ここで、電池ムは従来のカドミウムを含まない電池であ
る。これらの電池を用いて耐圧テストを行った結果を第
２表に示す。この値は電池の膨張量を示し、単位はｎで
ある。Table 1 However, mercury is 9% by weight. Here, the battery is a conventional cadmium-free battery. Table 2 shows the results of voltage resistance tests conducted using these batteries. This value indicates the amount of expansion of the battery, and its unit is n.
（以 下 余 白）
第２表より明らかなように電池の膨張は耐圧テストの電
圧に依存するが、一般にこの樵の二次電池で必要とされ
ている耐圧テス）１．７５Ｖ〜１．９０ Ｖで２０００
時間の基準で判断する時、電池ムおよびＢでは２０００
時間以内で電池の膨張が認められる。一方カドミウムの
含有量が６重量％以上である電池０ 、Ｄ 、ＩＣ、Ｆ
では膨張は認められなかった。このことは、合金中のカ
ドミウムの含有量が６重量％以上であれば、負極として
の酸素ガス吸収が効率良く行なわれたことを意味してい
ると考えられる。次に第３表は第１表のムからＦの電池
で同一亜鉛重量になるように合金量を調整した場合の放
電容量を示す。放電は１５にΩ。(Left below) As is clear from Table 2, the expansion of the battery depends on the voltage of the withstand voltage test, but the withstand voltage test (generally required for this woodcutter's secondary battery) is 1.75V to 1.90V. 2000 in V
When judging on the basis of time, 2000 for battery and B
Battery expansion is observed within hours. On the other hand, batteries 0, D, IC, F with a cadmium content of 6% by weight or more
No swelling was observed. This is considered to mean that when the cadmium content in the alloy was 6% by weight or more, oxygen gas absorption as a negative electrode was performed efficiently. Next, Table 3 shows the discharge capacity when the alloy amount is adjusted to have the same zinc weight in batteries M to F in Table 1. The discharge is 15Ω.
２０℃で終止電圧は１．３０ Ｖの条件である。The final voltage is 1.30 V at 20°C.
第３表
第３表より明らかなように、Ｆのカドミウムの含有量が
３０重量％になると、亜鉛の放電利用率が急速に低くな
ることがわかる。As is clear from Table 3, when the content of cadmium in F reaches 30% by weight, the discharge utilization rate of zinc rapidly decreases.
発明の効果
以上のように亜鉛と水銀とカドミウムよりなる合金にお
いて、合金に対するカドミウム含有量を５〜２０重量％
にすることによって、放電容量の大きな耐圧特性に優れ
た密閉型アルカリマンガン二次電池が得られた。Effects of the Invention As described above, in an alloy consisting of zinc, mercury, and cadmium, the cadmium content in the alloy is 5 to 20% by weight.
By doing so, a sealed alkaline manganese secondary battery with a large discharge capacity and excellent withstand voltage characteristics was obtained.
図は本発明の実施例における密閉型アルカリマ′ ンガ
ン二次電池の縦断面図である。
１・・・・・・正極ケース、２・・・・・・正極、３・
山・・正極リング、４・・・・・・セパレータ、６・川
・・含浸材、６・・・・・・封口リング、７・・・・・
・負極、８・・・・・・封口板。The figure is a longitudinal sectional view of a sealed alkaline manganese secondary battery in an embodiment of the present invention. 1...Positive electrode case, 2...Positive electrode, 3.
Mountain: Positive electrode ring, 4: Separator, 6: Impregnating material, 6: Sealing ring, 7...
・Negative electrode, 8...Sealing plate.
Claims (1)
アルカリ水溶液を電解液とした密閉型電池であって、前
記負極活物質が、亜鉛と水銀とカドミウムの合金であり
、かつカドミウム含有量が合金の５〜２０重量％である
ことを特徴とする密閉型アルカリマンガン二次電池。Manganese dioxide is the main positive electrode active material, zinc is the main negative electrode active material,
A sealed battery using an alkaline aqueous solution as an electrolyte, wherein the negative electrode active material is an alloy of zinc, mercury, and cadmium, and the cadmium content is 5 to 20% by weight of the alloy. type alkaline manganese secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61085384A JPS62243252A (en) | 1986-04-14 | 1986-04-14 | Sealed alkaline manganese secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61085384A JPS62243252A (en) | 1986-04-14 | 1986-04-14 | Sealed alkaline manganese secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62243252A true JPS62243252A (en) | 1987-10-23 |
Family
ID=13857242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61085384A Pending JPS62243252A (en) | 1986-04-14 | 1986-04-14 | Sealed alkaline manganese secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62243252A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6042704A (en) * | 1995-10-06 | 2000-03-28 | Ceramatec, Inc. | Storage-stable, fluid dispensing device using a hydrogen gas generator |
| US6060196A (en) * | 1995-10-06 | 2000-05-09 | Ceramtec, Inc. | Storage-stable zinc anode based electrochemical cell |
-
1986
- 1986-04-14 JP JP61085384A patent/JPS62243252A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6042704A (en) * | 1995-10-06 | 2000-03-28 | Ceramatec, Inc. | Storage-stable, fluid dispensing device using a hydrogen gas generator |
| US6060196A (en) * | 1995-10-06 | 2000-05-09 | Ceramtec, Inc. | Storage-stable zinc anode based electrochemical cell |
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