JPS62287578A - Enclosed alkaline storage battery - Google Patents
Enclosed alkaline storage batteryInfo
- Publication number
- JPS62287578A JPS62287578A JP61131521A JP13152186A JPS62287578A JP S62287578 A JPS62287578 A JP S62287578A JP 61131521 A JP61131521 A JP 61131521A JP 13152186 A JP13152186 A JP 13152186A JP S62287578 A JPS62287578 A JP S62287578A
- Authority
- JP
- Japan
- Prior art keywords
- charging
- battery
- cathode
- anode
- voltage
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 239000006182 cathode active material Substances 0.000 claims description 4
- 238000007600 charging Methods 0.000 abstract description 44
- 238000010281 constant-current constant-voltage charging Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 229910052793 cadmium Inorganic materials 0.000 description 12
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 12
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 238000010280 constant potential charging Methods 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 3
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010277 constant-current charging Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- HTQOEHYNHFXMJJ-UHFFFAOYSA-N oxosilver zinc Chemical compound [Zn].[Ag]=O HTQOEHYNHFXMJJ-UHFFFAOYSA-N 0.000 description 1
- 229910001923 silver oxide 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
- H01M10/34—Gastight 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
- Secondary Cells (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
〈産業上の利用分野〉
この発明は、電解液量制限型の密閉型アルカリ蓄電池に
関するものである。[Detailed Description of the Invention] 3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a sealed alkaline storage battery of a limited electrolyte amount type.
〈従来の技術）
ニッケルーカドミウム蓄電池ヤｊ酸化銀−亜鉛蓄電池あ
るいはニッケルー鉄蓄電池などのアルカリ蓄電池では、
カドミウムや亜鉛または鉄などを活物質として含有する
陰極板と、水駿化ニッケルや酸化銀などを活物質とする
陽極板とを用い、これらをセパレータを介して組合せて
収納缶に入れ、アルカリ電解液を注液するなどした構成
が採られている。<Prior art> In alkaline storage batteries such as nickel-cadmium storage batteries, silver oxide-zinc storage batteries, or nickel-iron storage batteries,
A cathode plate containing cadmium, zinc, or iron as an active material, and an anode plate containing nickel hydroxide, silver oxide, etc. as an active material are used, and these are combined through a separator and placed in a storage can to perform alkaline electrolysis. A configuration in which liquid is injected is adopted.
この種のアルカリ蓄電池、例えばニッケルーカドミウム
蓄電池では、充放電の際には下記の反応が起こり、また
満充電に達するとニッケル陽極からは酸素ガスが、カド
ミウム陰極からは水素ガスがそれぞれ発生する。In this type of alkaline storage battery, such as a nickel-cadmium storage battery, the following reactions occur during charging and discharging, and when the battery reaches full charge, oxygen gas is generated from the nickel anode and hydrogen gas is generated from the cadmium cathode.
そして、上記Ｍ素ガスはカドミウム陰極においてその充
電生成物である金属カドミウムと反応して電気化学的に
消費させることができるが、カドミウム陰極で発生する
水素ガスは電池内で・消費させることができず、電池容
器内に蓄積される。このため、過充電状態が長く続くと
水素ガス蓄積母が増大し電池容器の内圧が異常に上昇し
て、電池容器が変形したり安全弁の作動によってアルカ
リ電解液が外部漏出するといった不都合があり、電池の
密閉化が非常に困難であるといった欠点がある。The above M gas can be electrochemically consumed by reacting with metal cadmium, which is a charging product, at the cadmium cathode, but the hydrogen gas generated at the cadmium cathode cannot be consumed within the battery. Instead, it accumulates inside the battery container. For this reason, if the overcharge state continues for a long time, the hydrogen gas accumulation will increase and the internal pressure of the battery container will rise abnormally, causing problems such as deformation of the battery container and leakage of alkaline electrolyte to the outside due to the activation of the safety valve. The drawback is that it is very difficult to seal the battery.
この欠点を解潤するため、現用の密閉型のアルカリ蓄電
池では、陽極容量よりも陰極容量を実質的に大きくし、
充電時には陽極が陰極より先に満充電になるようにした
所謂陽極支配型の構成が採られている。この構成とする
ことで、充電末期に陽極が満充電になっても陰極は満充
電とならず、過充電状態におっても陽極からの酸素ガス
発生が優先して発生されるので、陰極からの水素ガス発
生が抑制されるようになる。In order to overcome this drawback, in current sealed alkaline storage batteries, the cathode capacity is substantially larger than the anode capacity.
During charging, a so-called anode-dominated configuration is adopted in which the anode is fully charged before the cathode. With this configuration, even if the anode is fully charged at the end of charging, the cathode will not be fully charged, and even in an overcharged state, oxygen gas will be generated from the anode with priority, so that oxygen gas will be generated from the cathode. hydrogen gas generation will be suppressed.
一方、現用の密閉型アルカリ蓄電池では、以上のことに
加えて、電池内に遊離の電解液が実質的に存在しないよ
うにその電解液量を制限する構成が用いられている。つ
まり、電池内の電解液量を多量にし、電解液中に電極体
を浸漬させたタイプの電池ではたとえ上］ホしたように
過充電時に先に陽極からの酸素ガス発生を優先させる構
成としても陽極で発生した閑素ガスは豊富な電解液に濡
れた陰極表面に到達することができず、上記消費反応に
よる電池内での酸素ガス消費ができなくなり、密閉型電
池であれば電池内部ガス圧が上昇してしまうからである
。On the other hand, in current sealed alkaline storage batteries, in addition to the above, a configuration is used in which the amount of electrolyte is limited so that there is substantially no free electrolyte in the battery. In other words, in a type of battery in which the amount of electrolyte in the battery is increased and the electrode body is immersed in the electrolyte, even if the configuration is such that the generation of oxygen gas from the anode is prioritized first during overcharging as shown in [e] above, The aerosol gas generated at the anode cannot reach the cathode surface, which is wet with the rich electrolyte, and oxygen gas cannot be consumed within the battery by the above consumption reaction, and in the case of a sealed battery, the internal gas pressure of the battery This is because the amount will rise.
〈発明が解決しようとする問題点〉
しかしながら、以上のように陽極支配型とした密閉型ア
ルカリ蓄電池では充電末期の電池電圧変化が小さいので
、充電完了を電圧変化によって捕えることが極めて難し
いという問題があり、このような電圧変化によって充電
を制御する回路を構成すると非常に複雑でそれ故高価な
ものとならざるを得ず、また例えば鉛蓄電池で一般に行
なわれている定電流一定電圧充電法をこの密閉型アルカ
リ蓄電池に実用上適用できないのである。<Problems to be Solved by the Invention> However, as described above, in an anode-dominated sealed alkaline storage battery, the battery voltage change at the end of charging is small, so there is a problem that it is extremely difficult to determine the completion of charging from the voltage change. However, configuring a circuit that controls charging using such voltage changes would be extremely complex and therefore expensive. It cannot be practically applied to sealed alkaline storage batteries.
また、この密閉型アルカリ蓄電池では、一般に、安全を
みこんで陰極容量を陽極容量よりもかなり大きく取って
設δ−１されており、電池放電容伍に実質的に貢献しな
い陰極部分を相当電池内に持ち込まざるを得ないため、
体積効率上非常に不利になるという問題がある。In addition, in this sealed alkaline storage battery, the cathode capacity is generally designed to be much larger than the anode capacity for safety reasons, and a considerable amount of the cathode portion, which does not substantially contribute to the battery discharge capacity, is kept inside the battery. Because we have no choice but to bring it into
There is a problem in that it is very disadvantageous in terms of volumetric efficiency.
〈問題点を解決するための手段〉
この発明の密閉型アルカリ蓄電池は、電池内に遊離の電
解液が実質的に存在しないように制限した電解液量制限
型のものであって、放電状態での陰極の未充電容量を陽
極の未充電容量よりも実質的に小さく構成したことを要
旨とする。<Means for Solving the Problems> The sealed alkaline storage battery of the present invention is of a type in which the amount of electrolyte is limited so that there is substantially no free electrolyte in the battery, and the amount of free electrolyte is limited in the battery in a discharged state. The gist is that the uncharged capacity of the cathode is substantially smaller than the uncharged capacity of the anode.
また、この構成に加えて、陰１※活物質より水素過電圧
の大きな全屈または金属化合物を陰極に添加・含有させ
てもよい。Further, in addition to this configuration, a total dielectric material or a metal compound having a larger hydrogen overvoltage than the cathode 1* active material may be added to and contained in the cathode.
〈作 用〉
従来の、陽極支配型で電解液量制限型の密閉型ニッケル
ーカドミウム蓄電池を用い、定電流で充電した場合の充
電量（％）に対する充電電圧（Ｖ）の変化を第５図に示
した。同図から、満充電時（充電量１００％近傍）にお
ける充電電圧の変化が極めて小さいことが明らかである
。<Function> Figure 5 shows the change in charging voltage (V) with respect to the amount of charge (%) when charging with a constant current using a conventional sealed nickel-cadmium storage battery with anode-dominated type and limited electrolyte volume. It was shown to. It is clear from the figure that the change in charging voltage at full charge (near 100% charge) is extremely small.
また、第６図はニッケル陽極（ＩＩ＞及びカドミウム陰
極（Ｉ＞の電極電位（ＶＶＳ ＨＣＪ／Ｈｇ０）をそ
れぞれ示したものであり、カドミウム陰極■は満充電時
に大きな電圧の立ら上がり（水素発生電位への立ち上が
り）を見せている。そして、上記従来の密閉型ニッケル
ーカドミウム蓄電池で満充電時に大きな電圧の立ち上が
りが見られないのは、この電池では、上述のように、陰
極より陽極の方が先に満充電になるように構成している
ため、陽極が満充電となり液量ガスを発生するようにな
ると、陰、極では前記酸素ガス消費反応が生じてそれ以
上充電が進行しなくなって陰極が見かけ上溝充電となる
ので、第６図で示した電位の立ら上がりが起こらないこ
とに起因している。Figure 6 shows the electrode potential (VVS HCJ/Hg0) of the nickel anode (II>) and the cadmium cathode (I>), and the cadmium cathode ■ has a large voltage rise (hydrogen generation) when fully charged. The reason why the above conventional sealed nickel-cadmium storage battery does not show a large voltage rise when fully charged is that, as mentioned above, the anode is closer to the anode than the cathode. Since the battery is configured so that it is fully charged first, when the anode becomes fully charged and begins to generate liquid gas, the oxygen gas consumption reaction occurs at the cathode and the electrode, and charging no longer progresses. This is because the cathode is apparently groove-charged, so the potential rise shown in FIG. 6 does not occur.
本発明の密閉型アルカリ蓄電池では上記のように構成し
たので、充電時には陰極が陽極よりも先に満充電となる
ため、陰極の水素発生電位への大きな立ら上がりによっ
て満充電時における電池充電電圧の電圧変化を大きくす
ることができる。Since the sealed alkaline storage battery of the present invention is constructed as described above, the cathode becomes fully charged before the anode during charging, so the battery charging voltage at full charge is reduced due to a large rise in the hydrogen generation potential of the cathode. The voltage change can be increased.
また、陰極活物質より水素過電圧の大きな金属または金
属化合物を陰極に添加することで、第６図で点線■で示
したように、陰極は満充電時により大きな電圧の立ち上
がりを示し、従って、上記の電池充電電圧の変化をより
大きくすることができる。In addition, by adding a metal or metal compound with a higher hydrogen overvoltage than the cathode active material to the cathode, the cathode exhibits a larger voltage rise when fully charged, as shown by the dotted line ■ in Figure 6, and therefore the above The change in battery charging voltage can be made larger.
そして、以上のように満充電時の電圧変化を大きくでき
るため、この電圧変化を利用して充電を制御することが
容易にできるようになり、前述の定電流一定電圧充電法
の適用も実用上可能となる。ただし、その場合、陰極の
水素発生電位が環境温度により変化するため、定電流充
電から定電圧充電に移行する際の制限電位として広い温
度範囲にわたって同一の電位を用いることが難しい場合
もめるが、上述のように陰極活物質より水素過電圧の大
きな金属または金属化合物（例えばカドミウム陰極の場
合にはＩｎやＺｎ）を添加することにより、これが改善
され、同一の制限電位を広い温度範囲にわたって使用す
ることが可能となる。第１図に、本発明の密閉型蓄電池
を定電流一定電圧充電した時の充電電流の典型的な変化
を示した。As described above, since the voltage change during full charging can be increased, charging can be easily controlled using this voltage change, making it practical to apply the constant current constant voltage charging method described above. It becomes possible. However, in that case, since the hydrogen generation potential of the cathode changes depending on the environmental temperature, it may be difficult to use the same potential over a wide temperature range as the limiting potential when transitioning from constant current charging to constant voltage charging, but as mentioned above, This can be improved by adding a metal or metal compound (for example, In or Zn in the case of a cadmium cathode) that has a higher hydrogen overvoltage than the cathode active material, making it possible to use the same limiting potential over a wide temperature range. It becomes possible. FIG. 1 shows typical changes in charging current when the sealed storage battery of the present invention is charged with constant current and constant voltage.
また、電池放電容量に実質的に貢献しない陰極容量を大
幅に減らし、その分陽極容量並びに電池放電容量に貢献
する陰極部分を増やすことができるので電°池の体積効
率が大幅に改善される。Furthermore, the cathode capacity that does not substantially contribute to the battery discharge capacity can be significantly reduced, and the anode capacity and the cathode portion that contribute to the battery discharge capacity can be increased by that amount, so that the volumetric efficiency of the battery can be greatly improved.
〈実施例〉
以下にこの発明をニッケルーカドミウム蓄電池に適用し
た例を説明する。<Example> An example in which the present invention is applied to a nickel-cadmium storage battery will be described below.
実害ｆ４１８００ｍＡＨの焼結式ニッケル陽極と、実容
量１５００ｍＡＨの焼結式カドミウム陰極とを、夫々放
電状態でセパレータを介して組合せ、これらを−緒に捲
回して電極体を構成した。この電極体を電池外装缶に入
れ、２５重量％の水酸化カリウム水溶液をアルカリ電解
液として５ＣＣ注液し、その後外装缶開口を封口して電
解液量制限型の密閉型ニッケルーカドミウム蓄電池（本
発明電池Ａ：公称容量１５００ｍＡＨ）を作製した。A sintered nickel anode with an actual damage f of 41,800 mAH and a sintered cadmium cathode with an actual capacity of 1,500 mAH were combined in a discharge state via a separator, and then wound together to form an electrode body. This electrode body is placed in a battery outer can, and 5cc of 25% by weight potassium hydroxide aqueous solution is injected as an alkaline electrolyte.Then, the opening of the outer can is sealed and the electrolyte amount is limited to a sealed nickel-cadmium storage battery. Invention battery A (nominal capacity: 1500 mAH) was produced.
この電池に用いたカドミウム陰極並びにニッケル陽極の
夫々の極板容量を第３図（Ａ）に模式的に示した。The plate capacities of the cadmium cathode and nickel anode used in this battery are schematically shown in FIG. 3(A).
第３図（Ｂ）は同型に構成した従来の密閉型ニッケルー
カドミウム蓄電池（従来電池Ｂ）に用いるカドミウム陰
極及びニッケル陽極の各極板容量の模式図である。図中
、斜線部は充電状態の容量を、また白色部は放電状態の
容量を指す。FIG. 3(B) is a schematic diagram of the capacity of each plate of a cadmium cathode and a nickel anode used in a conventional sealed nickel-cadmium storage battery (conventional battery B) configured in the same manner. In the figure, the shaded area indicates the capacity in the charged state, and the white area indicates the capacity in the discharged state.
この電池では公称容量は１２００ｍＡＨとなっており、
本発明電池へでは従来電池の１２５％の公称容量をもた
せることができた。This battery has a nominal capacity of 1200mAH.
The battery of the present invention was able to have a nominal capacity of 125% of that of the conventional battery.
また、第４図に示したように、実容量 １８００ｍＡＨ
の焼結式ニッケル陽極と、実害ｆｆ１１８００ｍＡＨで
３００ｍＡＨに相当する容量を先に充電した焼結式カド
ミウム陰極とを用いて電解液量制限型の密閉型ニッケル
ーカドミウム蓄電池（本発明電池Ｃ：公称容量１５００
ｍＡＨ＞を作製した。In addition, as shown in Figure 4, the actual capacity is 1800mAH.
A sealed nickel-cadmium storage battery with a limited amount of electrolyte (invention battery C: nominal capacity) is constructed using a sintered nickel anode of 1500
mAH> was produced.
これら３つの電池の体積効率（ｍＡＨ／ｃｃ）を第１表
に示した。The volumetric efficiencies (mAH/cc) of these three batteries are shown in Table 1.
第１表
また、上記本発明電池Ａ、Ｃについて、それぞれ１０時
間率（０，ＩＣ＞の電流で充電した所、満充電時にはそ
れぞれ、従来電池Ｂには見られなかった鋭い充電電圧の
立ち上がりが見られた。Table 1 Also, when batteries A and C of the present invention were charged at a current of 10 hours (0, IC), a sharp rise in charging voltage, which was not observed in conventional battery B, was observed when fully charged. It was seen.
更に、上記２つの電池Ａ、Ｃを第２表の条件で環境温度
０’Ｃ，２０’Ｃ，５０℃でそれぞれ定電流一定電圧充
電テストを行なった。Further, the two batteries A and C were subjected to constant current and constant voltage charging tests at environmental temperatures of 0'C, 20'C, and 50C under the conditions shown in Table 2, respectively.
第２表
テスト結果は第２図に示した通りであり、２０’Ｃでは
それぞれ図中実線ａのように満充電時からは充電電流が
減少していく正常な充電が行なわれた。また、温度５０
’Ｃでは一点鎖線すのように、充電電流は満充電時から
一度は減少するものの、再び増大して結局過充電状態に
なってしまった。これは、満充電後に流れる充電電流に
よる電解で電池温度が更に上昇し、満充電後の電池充電
電圧が温度上昇によって低下して制限電圧以下となり占
び定電圧充電に戻っていったためであり、満充電時の電
圧の立ち上がりの度合がやや小さいことが原因であると
考えられる。一方、温度Ｏ℃では点線Ｃで示したように
充電初期より充電電流が減少していき、充電不足となっ
た。これは充電初期から電池充電電圧が制限電位に到達
していたため、はじめから定電圧充電になってしまった
ことに依る。The test results in Table 2 are as shown in FIG. 2, and at 20'C, normal charging was performed in which the charging current decreased from the time of full charge, as indicated by the solid line a in the figure. Also, the temperature is 50
In 'C, as shown by the dashed-dotted line, the charging current decreases once from full charge, but increases again and eventually becomes overcharged. This is because the battery temperature further rises due to electrolysis caused by the charging current that flows after full charge, and the battery charging voltage after full charge decreases due to the temperature rise, becoming below the limit voltage and returning to constant voltage charging. This is thought to be because the degree of voltage rise during full charge is somewhat small. On the other hand, at a temperature of 0° C., as shown by the dotted line C, the charging current decreased from the initial stage of charging, resulting in insufficient charging. This is because the battery charging voltage had reached the limiting potential from the beginning of charging, resulting in constant voltage charging from the beginning.
また、活物質として酸化カドミウムを用い、また酸化カ
ドミウムに対して０．５〜１重足％の酸化インジウムを
添加し、これらを糊料とともに混練して作った活物質ペ
ーストを集電体に塗着して作製したペース１〜式カドミ
ウム陰極を用いた他は本発明電池Ａと同様な密閉型のニ
ッケルーカドミウム蓄電池（本発明電池Ｄ）を作った。In addition, cadmium oxide is used as an active material, and 0.5 to 1% indium oxide is added to cadmium oxide, and an active material paste made by kneading these with a glue is applied to the current collector. A sealed nickel-cadmium storage battery (Battery D of the present invention) similar to Battery A of the present invention was made except that the cadmium cathode of the PACE 1~ type prepared by the above method was used.
更に、酸化インジウムに代えて酸化亜鉛を、酸化カドミ
ウムに対して０．２〜５重量％添加した他は本発明電池
りと同様な密閉型ニッケルーカドミウム蓄電池（本発明
電池Ｅ）を作った。Furthermore, a sealed nickel-cadmium storage battery (Battery E of the present invention) similar to the battery of the present invention was prepared except that 0.2 to 5% by weight of zinc oxide was added to the cadmium oxide instead of indium oxide.
これら２つの電池り、Ｅをそれぞれ１０Ｒｉ！間率（０
，ＩＣ＞の電流で充電した所、満充電時の電池充電電圧
の立ち上がりは、酸化インジウムあるいは酸化亜鉛の無
添加の場合に較べて、ともに２００〜２５０ｍＶ増大し
た。These two batteries each have 10 Ri! Space rate (0
, IC>, the rise of the battery charging voltage at full charge increased by 200 to 250 mV compared to the case where no indium oxide or zinc oxide was added.
次に、これら電池り、Ｅを第３表の条件で上記、電池Ａ
、Ｃの場合と同様に定電流一定電圧充電テス１〜を行な
った。Next, these batteries, E, and the above battery A under the conditions shown in Table 3.
As in the case of , C, constant current constant voltage charging tests 1 to 1 were conducted.
テストの結果は、温度Ｏ℃、２０℃、５０℃のいずれの
温度においても充電電流は第２図の実線Ｃで示した変化
を示し、すべて正常な充電を行なえた。As a result of the test, the charging current showed the change shown by the solid line C in FIG. 2 at all temperatures of 0° C., 20° C., and 50° C., and normal charging was possible in all cases.
〈発明の効果〉
以上のように構成されるこの発明のアルカリ蓄電池によ
れば、満充電時の電池充電電圧の立ち上がりを大きくで
きるため、満充電時の電圧変化を容易且つ確実に検知で
き、従来電池では実用上適用不可能であった定電流一定
電圧充電が行なえる。また、陰極活物質より水素過電圧
が大きい金属または金属化合物を陰極に添加することで
、広い温度範囲での定電流一定電圧充電が可能となる。<Effects of the Invention> According to the alkaline storage battery of the present invention configured as described above, since the rise of the battery charging voltage at full charge can be increased, voltage changes at full charge can be easily and reliably detected, which is different from conventional Constant-current, constant-voltage charging, which is practically impossible with batteries, can be performed. Further, by adding a metal or a metal compound having a higher hydrogen overvoltage than the cathode active material to the cathode, constant current and constant voltage charging becomes possible over a wide temperature range.
更に、従来電池と較べて、陰極の実質容量を大幅に小さ
くできるので、電池充電電圧の増大を図り、体積効率の
よい電池を提供することができる。Furthermore, since the actual capacity of the cathode can be significantly reduced compared to conventional batteries, it is possible to increase the battery charging voltage and provide a battery with good volumetric efficiency.
第１図は本発明の電池を定電流一定電圧充電した時の典
型的な充電電流の変化を示したグラフ、第２図は同じく
充電時の環境温度を変えた場合の充電電流の変化を示し
たグラフ、第３図（＾）、 （Ｂ）及び第４図は本発明
電池及び従来電池の極板容母の模式図、第５図は従来電
池の充電電圧の変化を示したグラフ、第６図は同じく電
極電位の変化を示したグラフである。
第１図
第２図
先 電 量 （％）
ｆａ３図
第４図
第５図
１１１１％）
先電量（％）Figure 1 is a graph showing typical changes in charging current when the battery of the present invention is charged with constant current and voltage, and Figure 2 is a graph showing changes in charging current when the environmental temperature during charging is changed. The graphs shown in Figures 3 (^), (B) and Figure 4 are schematic diagrams of the electrode plate bodies of the battery of the present invention and the conventional battery, and Figure 5 is a graph showing changes in charging voltage of the conventional battery. FIG. 6 is a graph similarly showing changes in electrode potential. Fig. 1 Fig. 2 Amount of electricity (%) Fig. 3 Fig. 4 Fig. 5 1111%) Amount of electricity (%)
Claims (1)
制限した電解液量制限型のものであって、放電状態での
陰極の未充電容量を陽極の未充電容量よりも実質的に小
さく構成したことを特徴とする密閉型アルカリ蓄電池。 ２、陰極活物質より水素過電圧が大きい金属または金属
化合物を陰極に添加・含有させたことを特徴とする特許
請求の範囲第１項記載の密閉型アルカリ蓄電池。[Scope of Claims] 1. An electrolyte amount-limiting type battery in which the amount of electrolyte is limited so that there is substantially no free electrolyte in the battery, and the uncharged capacity of the cathode in a discharged state is equal to the uncharged capacity of the anode. A sealed alkaline storage battery characterized by being configured to be substantially smaller than its capacity. 2. The sealed alkaline storage battery according to claim 1, wherein a metal or a metal compound having a higher hydrogen overvoltage than the cathode active material is added to and contained in the cathode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61131521A JPH0644491B2 (en) | 1986-06-06 | 1986-06-06 | Sealed alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61131521A JPH0644491B2 (en) | 1986-06-06 | 1986-06-06 | Sealed alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62287578A true JPS62287578A (en) | 1987-12-14 |
| JPH0644491B2 JPH0644491B2 (en) | 1994-06-08 |
Family
ID=15059998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61131521A Expired - Lifetime JPH0644491B2 (en) | 1986-06-06 | 1986-06-06 | Sealed alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0644491B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5716471A (en) * | 1980-07-03 | 1982-01-27 | Ricoh Co Ltd | Controller for tonor density |
| JPS58131668A (en) * | 1982-01-30 | 1983-08-05 | Matsushita Electric Ind Co Ltd | Rechargeable silver oxide cell |
| JPS6191882A (en) * | 1984-10-12 | 1986-05-09 | Asahi Glass Co Ltd | Metal oxide-hydrogen secondary battery |
-
1986
- 1986-06-06 JP JP61131521A patent/JPH0644491B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5716471A (en) * | 1980-07-03 | 1982-01-27 | Ricoh Co Ltd | Controller for tonor density |
| JPS58131668A (en) * | 1982-01-30 | 1983-08-05 | Matsushita Electric Ind Co Ltd | Rechargeable silver oxide cell |
| JPS6191882A (en) * | 1984-10-12 | 1986-05-09 | Asahi Glass Co Ltd | Metal oxide-hydrogen secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0644491B2 (en) | 1994-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0354966B1 (en) | Alkaline secondary battery and process for its production | |
| KR102039205B1 (en) | Management of gas pressure and electrode state of charge in alkaline batteries | |
| GB1472695A (en) | Hermetically sealed alkaline storage batteries | |
| US5569554A (en) | Sealed rechargeable battery with stabilizer | |
| JPS5928027B2 (en) | Rechargeable chemical battery or storage battery | |
| JPS5832473B2 (en) | Manufacturing method of sealed nickel-cadmium alkaline storage battery | |
| JP2001176455A (en) | Cylindrical secondary battery | |
| KR20000069898A (en) | Alkaline storage battery and method for charging battery | |
| JPS62287578A (en) | Enclosed alkaline storage battery | |
| JP2000150000A (en) | Backup power supply control method | |
| JP2962326B1 (en) | Nickel-hydrogen storage battery for backup power supply | |
| US3457111A (en) | Alkaline storage battery with be(oh)2 in the electrolyte | |
| JPH042065A (en) | Secondary battery with non-aqueous electrolyte and manufacture thereof | |
| JPS60198066A (en) | Alkaline storage battery | |
| JPH09204931A (en) | Method of charging sealed nickel hydrogen secondary battery, and charging device thereof | |
| JPS635866B2 (en) | ||
| KR870001471B1 (en) | Solid battery | |
| JPH0544784B2 (en) | ||
| JPH028419B2 (en) | ||
| JPH05307973A (en) | Chemical conversion charging method of nickel-cadmium battery | |
| JP2001076753A (en) | Nickel-hydrogenized metal sealed storage battery | |
| JPH038269A (en) | Alkaline secondary battery | |
| JPH0665067B2 (en) | Nickel zinc battery | |
| JPS6351350B2 (en) | ||
| JPH0443571A (en) | Sealed nickel-cadmium battery and manufacture thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |