JPS63213263A - Lead storage battery - Google Patents
Lead storage batteryInfo
- Publication number
- JPS63213263A JPS63213263A JP62044802A JP4480287A JPS63213263A JP S63213263 A JPS63213263 A JP S63213263A JP 62044802 A JP62044802 A JP 62044802A JP 4480287 A JP4480287 A JP 4480287A JP S63213263 A JPS63213263 A JP S63213263A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- overdischarge
- compound
- electrolyte
- alkaline earth
- 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
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910000978 Pb alloy Inorganic materials 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 21
- 239000000956 alloy Substances 0.000 abstract description 21
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 4
- 238000007600 charging Methods 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 2
- 229910000838 Al alloy Inorganic materials 0.000 abstract 1
- 229910000882 Ca alloy Inorganic materials 0.000 abstract 1
- 229910014474 Ca-Sn Inorganic materials 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 230000007423 decrease Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910001245 Sb alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- -1 halogen ions Chemical class 0.000 description 2
- 230000036647 reaction Effects 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910020669 PbOx Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910002058 ternary alloy 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
- H01M4/685—Lead alloys
-
- 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
- H01M10/06—Lead-acid 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は鉛蓄ｔ′池の自己放電性能、長期保存性能や過
放電放置性向上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 the self-discharge performance, long-term storage performance, and overdischarge resistance of lead-acid T' batteries.
従来の技術
鉛蓄電池は、長期間放置されたり、また過放電の状態で
放置されたりすると自己放電により、充電不可能な状態
になり、早期に寿命となる場合か極めて多い。そこで従
来このような状態に陥らないようにするために、鉛蓄電
池の格子合金に関して工夫かなされており１例えば格子
体のアンチモン含有量を減らして自己放電を減少させた
り、アンチそンを含有しない合金としてＰｂ−０ａ系合
金を使用して自己放電を減少させている。また、過放電
放置性能を低下させる原因である格子−活物質界面のＰ
ｂＯｘや硫酸鉛生成を防止するために格子表面に導電体
をコーティングしたり、上記の高抵抗体か生成しても導
通が維持されるように活物質中にペロブスカイト系の化
合物や銀粉を分散せしめた導電性樹脂を添加したり、電
解液液中にリン酸やアルカリ金属イオンを添加させたり
している。If conventional lead-acid batteries are left unused for a long period of time or left in an over-discharged state, they will self-discharge and become unrechargeable, resulting in premature end of their service life. In order to avoid this situation, conventional methods have been devised regarding the lattice alloy of lead-acid batteries.1 For example, the antimony content of the lattice is reduced to reduce self-discharge, or the lattice alloy does not contain antimony. A Pb-0a alloy is used as the alloy to reduce self-discharge. In addition, P at the lattice-active material interface, which is the cause of deteriorating overdischarge performance.
In order to prevent the formation of bOx and lead sulfate, the lattice surface is coated with a conductor, and a perovskite compound or silver powder is dispersed in the active material so that conductivity is maintained even if the above-mentioned high-resistance substances are formed. In some cases, conductive resin is added, or phosphoric acid or alkali metal ions are added to the electrolyte solution.
発明か解決しようとする問題点
現在実用化されている格子合金はｐｂ−ｓｂ系とＰｂ−
０ａ系であるが、ｓｂ系はｓｂの水素発生電位が責なた
め自己放電が大きく、また充電中に水電解電圧が小さい
ので水の減少量が多くなる欠点がある。一方、Ｐｂ−Ｏ
ａ合金では深い充放電サイクル使用においては寿命が短
かくなり、過放電防止のための特別な負荷回路が必要と
なり、電池以外の回路システムがコスト面で実用性を乏
しくしている。また、Ｓｂ含有ヱを減少させても３．５
重ｆ１４以下ではＳｂを含有しない合金と同様の欠点を
有する。したがってＰｂ−０ａ、ｐｂ−ｓｂの２元素格
子合金組成だけでは問題点を解決しに（い。そこで、近
年、このような点からＰｂ−８ｎ−Ａｓ、Ｐｂ−０ａ−
８ｎの３元系合金が提案されている。Problems to be solved by the invention The lattice alloys currently in practical use are pb-sb and Pb-
Although it is a 0a type, the sb type has a drawback that self-discharge is large due to the hydrogen generation potential of sb, and the amount of water lost is large because the water electrolysis voltage is low during charging. On the other hand, Pb-O
A-alloys have short lifespans when used in deep charge/discharge cycles, and a special load circuit is required to prevent overdischarge, making circuit systems other than batteries impractical in terms of cost. Moreover, even if the Sb content is reduced, 3.5
If the weight is less than f14, it has the same drawbacks as alloys that do not contain Sb. Therefore, it is difficult to solve the problem with only the two-element lattice alloy composition of Pb-0a and pb-sb.
A ternary alloy of 8n has been proposed.
これらの合金は自己放電か小さく、水分解もｐｂ−ａａ
合金並であり、Ｓｎを含有しているので適数ｔ”放置特
性も良好である。しかし、過放電されると電解液である
硫酸濃度が著しく低下してその結果、液の伝導度も著し
く低下するためやはり、充電不可能となる。したかって
。These alloys have low self-discharge and water decomposition is pb-aa
It is comparable to alloys and contains Sn, so it has good storage properties for a suitable number of hours. However, when over-discharged, the concentration of sulfuric acid, which is the electrolytic solution, decreases significantly, and as a result, the conductivity of the solution also decreases significantly. As expected, it becomes impossible to charge.
格子合金だけでなく、電解液の伝導性維持が問題点とし
て上げられる。従来この点について、Ｈ，ＰＯ，を電解
液中に添加することやアルカリ金属イオンの添加が考え
られてきたが、ＨｌＰＯ，は過放電時の充電性は改養さ
れるものの。In addition to the lattice alloy, maintaining the conductivity of the electrolyte is a problem. Conventionally, in this regard, it has been considered to add H, PO, or alkali metal ions to the electrolytic solution, but although HlPO improves the charging performance during overdischarge.
寿命初期時の放電容量が低下し、また自己放電はむしろ
太き（なる。また、アルカリ金属はコスト面で高（なる
（特に硫酸塩）。The discharge capacity at the beginning of life decreases, and the self-discharge becomes rather thick.Also, alkali metals are expensive (especially sulfates).
問題点を解決するための手段
そこで、上記の欠点をすべて解決するために、本発明者
らは、減液性が小さく、自己放電の小さくかつ過放電放
置特性のよいＰｂ−０ａ−８ａ合金およびＰｂ−０ａ−
８ｎ−ｓｂ金合金Ｐｂ−０ａ−８ｎ−８ｂ−Ａ、、ｇ合
金ノイずれカッ合金からなる極板基体を用い、一方、電
解液の伝導度維持については、アルカリ土類金属イオン
を存在させ、これらの組合せから構成される鉛蓄電池に
おいてはその相乗効果によって過放電放置特性か良好に
なることを見い出した。Means for Solving the Problems Therefore, in order to solve all of the above-mentioned drawbacks, the present inventors developed a Pb-0a-8a alloy and a Pb-0a-8a alloy that have low liquid-reducing properties, low self-discharge, and good overdischarge characteristics. Pb-0a-
An electrode plate base made of 8n-sb gold alloy Pb-0a-8n-8b-A, and g alloy Noisekat alloy was used, and on the other hand, to maintain the conductivity of the electrolyte, alkaline earth metal ions were present, It has been found that a lead-acid battery composed of a combination of these has good overdischarge characteristics due to the synergistic effect.
作用
鉛蓄電池は充電せずに長期間放置すると自己放電により
充電不能な状態になり、また深い放電後放置されると同
様に充電不能な状態となる。If a lead-acid battery is left uncharged for a long period of time, it will become unrechargeable due to self-discharge, and if it is left uncharged after deep discharge, it will also become unrechargeable.
この原因としては、正極板の内部抵抗か著しく上昇する
ためであり、その上昇させる要因は恐らく次の様に考え
られる。鉛蓄電池か過放電されると電解液比重か低下し
、極板内部の基体近傍では表面に比べてさらに低下して
いる この場合基体のｐｂの溶解度が上昇し、Ｐｂ
か生成すると正極基体近傍の活物質であるｐｂｏｔはＰ
Ｈか高くなると不安定になり１局部電池反応を形成し、
Ｐ ｂ Ｏｔ ＋ Ｐ ｂ ＋ ２ Ｈｔ Ｓ Ｏａ
→２ＰｂＳＯ，＋２Ｈ，ＯとなってＰｂ８０．を生成す
る。同時にＰｂ５Ｏ，はＰＨか高いと溶解析出をくり返
して結晶が成長し、非還元性のｐｂｓｏ、が基体界面を
被覆するようになる。The reason for this is that the internal resistance of the positive electrode plate increases significantly, and the factors that cause this increase are probably as follows. When a lead-acid battery is over-discharged, the specific gravity of the electrolyte decreases, and it decreases even further near the substrate inside the electrode plate compared to the surface.In this case, the solubility of PB in the substrate increases, and Pb
When generated, pbot, which is an active material near the positive electrode substrate, becomes P
When H becomes high, it becomes unstable and forms a local cell reaction,
P b Ot + P b + 2 Ht S Oa
→2PbSO, +2H, O becomes Pb80. generate. At the same time, when the pH is high, Pb5O repeats dissolution precipitation and crystals grow, so that non-reducible PbSO coats the substrate interface.
さらには、上記局部電池反応でＨ，８０，が消費される
と正極電位が低下して−４００〜−２００ｍＶ （ＶＳ
、ＨＰ／Ｈｙ、８０４ ）ぐらいまで卑になる。この電
位では、さらにＰｂＯ。Furthermore, when H,80, is consumed in the above local battery reaction, the positive electrode potential decreases to -400 to -200 mV (VS
, HP/Hy, 804). At this potential, additional PbO.
（活物質） ＋Ｈ，０＋ ２ ｅ−＋Ｐ ｂ Ｏ（Ｐ
ｂ Ｏｘ）＋２０Ｈ−とｐｂ（極板基体）＋ＳＯ番ト→
Ｐｂ５Ｏ＊＋２ｅの局部電池反応が相乗して生ずるよう
になり （Ｅ＊ −−３７０ｍｖ ｖｓ、Ｈ７／Ｈｐ
ｌ ８０．”） 、Ｐｂ５Ｏ，の成長とＰｂＯｘの生成
によって高抵抗皮膜が形成され、つまるところ充電不能
に陥いる。そこで、これらの高抵抗皮膜か形成しにくい
。または形成してもｂ（極板基体）とｐｂＯｔ（活物質
）とが導通させる化合物か存在すればよい。８ｎはこの
ような過放電放置に対して効果のあることが従来指上げ
た。この効果については明確にされていないか、Ｐｂマ
トリックス中にＣａ１ｎ、 、または、ＰｂｘＯａｙＳ
ｎｚなる金属間化合物か生成し、極板基体かアノード酸
化されるとこれが酸化皮膜中に分散して導電性が保持さ
れているか、またはＳｎが酸化されて、８ｎＯや８ｎＯ
。(Active material) +H,0+ 2 e-+P b O(P
b Ox) + 20H- and pb (electrode plate base) + SO number →
The local cell reaction of Pb5O*+2e started to occur synergistically (E* −-370mv vs, H7/Hp
l 80. ”), Pb5O, and the formation of PbOx, a high-resistance film is formed, which ultimately leads to the inability to charge.Therefore, it is difficult to form these high-resistance films.Or, even if they are formed, the b (electrode plate substrate) It is only necessary that there is a compound that allows conduction with pbOt (active material). It has been suggested that 8n is effective against such overdischarge.This effect has not been clarified, or the Pb matrix Ca1n, or PbxOayS in
An intermetallic compound called nz is generated, and when the electrode plate substrate is anodically oxidized, this is dispersed in the oxide film and conductivity is maintained, or Sn is oxidized and becomes 8nO or 8nO.
.
のような化合物となり、これが半導体的性質（ｎ型半導
体）を有することにより充電性がよ化皮膜中に存在する
とｓｂｏ、となって存在したり、アンチモン酸イオンと
なって溶出して高抵抗体皮膜をやぶつ、多孔質なものに
する性質Ａ４についてはＰｂ−０ａ−Ｓｂ系合金ではＣ
ａとｓｂの重［４が増大するとＣａとｓｂかＯａｔ Ｓ
ｂｓとなるドロス化合物を生成させて固溶化しない。こ
の場合Ａ４が存在するとＯａはドロス化せず合金中に固
定されるため、ｐｂ−Ｏａ−Ｓｂ系合金においてＡ影の
添加は効果かある。This compound has semiconducting properties (n-type semiconductor), so if it exists in a cured film, it will exist as sbo, or it will elute as antimonate ions, forming a high-resistance material. Regarding property A4 that makes the film coarse and porous, in Pb-0a-Sb alloy, C
When the weight of a and sb [4 increases, Ca and sb or Oat S
A dross compound that becomes bs is not generated and converted into a solid solution. In this case, when A4 is present, Oa does not turn into dross and is fixed in the alloy, so the addition of A shadow is effective in pb-Oa-Sb alloys.
一方、電解液中の添加物については、充電では、正極側
で酸化反応が生じ、電子が負荷側へ流れ、を解液中では
、Ｈ＋、８０Ｆ−によって負極から電荷を担ってくる。On the other hand, regarding the additives in the electrolytic solution, during charging, an oxidation reaction occurs on the positive electrode side, and electrons flow to the load side, and in the electrolytic solution, charges are carried from the negative electrode by H+ and 80F-.
しかし、過放電後はＰＨが７近傍になるのでＨ，Ｏが増
加し、ｓｏ、’−もＨ”４少なくなる。したがって電荷
の担手としてＳＯニー塩のカチオンが必要となること、
またアニオンはハロゲンイオンやＮＯ１！−のようにｐ
ｂと反応してしまうものが多いので、カチオンの中から
選択しなければならない。なかでも電池の他の性能（寿
命、容量）への影響を考慮し、硫酸塩をつくるものの中
で選ぶべきである。However, after overdischarge, the pH becomes around 7, so H and O increase, and so,'- also decreases by H''4. Therefore, the cation of the SO knee salt is required as a charge carrier.
Also, anions are halogen ions and NO1! - as in p
Since many react with b, it must be selected from among cations. Among these, you should choose one among those that produce sulfates, taking into consideration the effect on other battery performance (life, capacity).
第１表は種々の硫酸塩の２５°Ｃにおけるイオン伝導度
を示している力ζその中でアルカリ土類金属が良好と考
えられるのでこれを選択した。Table 1 shows the ionic conductivities of various sulfates at 25°C.Among them, alkaline earth metals were selected because they are considered to be good.
またアルカリ金属よりもアルカリ土類金属はコスト面で
安価である。Furthermore, alkaline earth metals are cheaper than alkali metals.
第 １ 表 実施例 本発明の一実施例について説明する。Table 1 Example An embodiment of the present invention will be described.
Ｐｂ−０ａ合金にＳｎを含有させ、さらにｓｂやＡ４を
含有させた格子を作製し、電解液中にアルカリ土類金属
としてＭ７ＳＯ，を所定し、２４時間後開路状態にして
、１ケ月放置後（２５°Ｃ）、充電回復（２，４５Ｖ／
セル定電圧充電）シて初期５時間率容量と回復容量との
比率を測定した。比較のためにＰｂ−０ａ合金と無添加
の電解液の場合を示した第１図から、Ｐｂ−０ａ、Ｐｂ
−０ａ−８ｎ、Ｐｂ−０ａ−８ｎ−８ｂ、Ｐｂ−０ａ−
８ｎ−８ｂ −Ａ４合金の電解液中無添加のものは容量
回復率が下回ることかわかる。これは本発明において、
Ｓ ｎ＋ｓｂの効果とＭ７ＳＯ，の効果か相乗的に現わ
れ、過放電放置による高抵抗体の生成を抑制したためと
考えられる。A lattice made of Pb-0a alloy containing Sn and further containing sb and A4 was prepared, and M7SO was predetermined as an alkaline earth metal in the electrolyte. After 24 hours, the circuit was opened, and after being left for one month. (25°C), charge recovery (2,45V/
The ratio between the initial 5-hour rate capacity and the recovery capacity was measured by cell constant voltage charging. For comparison, from Figure 1, which shows the case of Pb-0a alloy and additive-free electrolyte, Pb-0a, Pb
-0a-8n, Pb-0a-8n-8b, Pb-0a-
It can be seen that the capacity recovery rate of the 8n-8b-A4 alloy with no additives in the electrolyte is lower. In the present invention, this
This is thought to be because the effect of S n + sb and the effect of M7SO appeared synergistically, suppressing the formation of a high resistance object due to overdischarge.
発明の効果
上述したように、本発明によれば、過放電放置特性か改
善され、実用に供し得る鉛蓄電池を提供することができ
る点工業的価値甚だ大なるものである。Effects of the Invention As described above, the present invention has great industrial value in that it can provide a lead-acid battery which has improved over-discharge characteristics and can be put to practical use.
４ Ｍ面の節■か忙凹
第１図は本発明の一実施例における容量回復率を示す比
較図である。Figure 1 is a comparative diagram showing the capacity recovery rate in one embodiment of the present invention.
Claims (1)
を用いかつ、電解液中にアルカリ土類金属イオンが存在
する鉛蓄電池。[Claims] A lead-acid battery using an electrode plate base made of Ca and Sn or a lead alloy containing Ca, Sn, Sb, or Ca, Sn, Sb, and Al, and in which alkaline earth metal ions are present in the electrolyte. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62044802A JPS63213263A (en) | 1987-02-27 | 1987-02-27 | Lead storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62044802A JPS63213263A (en) | 1987-02-27 | 1987-02-27 | Lead storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63213263A true JPS63213263A (en) | 1988-09-06 |
Family
ID=12701555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62044802A Pending JPS63213263A (en) | 1987-02-27 | 1987-02-27 | Lead storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63213263A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0346768A (en) * | 1989-07-13 | 1991-02-28 | Matsushita Electric Ind Co Ltd | Lead storage battery |
| WO2009142220A1 (en) * | 2008-05-20 | 2009-11-26 | 株式会社ジーエス・ユアサコーポレーション | Lead storage battery and process for producing the lead storage battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58117658A (en) * | 1981-12-29 | 1983-07-13 | Matsushita Electric Ind Co Ltd | Sealed lead-acid battery |
| JPS5929383A (en) * | 1982-08-12 | 1984-02-16 | Shin Kobe Electric Mach Co Ltd | Sealed lead storage battery |
| JPS609065A (en) * | 1983-06-28 | 1985-01-18 | Shin Kobe Electric Mach Co Ltd | Sealed lead storage battery |
-
1987
- 1987-02-27 JP JP62044802A patent/JPS63213263A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58117658A (en) * | 1981-12-29 | 1983-07-13 | Matsushita Electric Ind Co Ltd | Sealed lead-acid battery |
| JPS5929383A (en) * | 1982-08-12 | 1984-02-16 | Shin Kobe Electric Mach Co Ltd | Sealed lead storage battery |
| JPS609065A (en) * | 1983-06-28 | 1985-01-18 | Shin Kobe Electric Mach Co Ltd | Sealed lead storage battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0346768A (en) * | 1989-07-13 | 1991-02-28 | Matsushita Electric Ind Co Ltd | Lead storage battery |
| WO2009142220A1 (en) * | 2008-05-20 | 2009-11-26 | 株式会社ジーエス・ユアサコーポレーション | Lead storage battery and process for producing the lead storage battery |
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