JP2808685B2 - Lead storage battery - Google Patents

Lead storage battery

Info

Publication number
JP2808685B2
JP2808685B2 JP1181054A JP18105489A JP2808685B2 JP 2808685 B2 JP2808685 B2 JP 2808685B2 JP 1181054 A JP1181054 A JP 1181054A JP 18105489 A JP18105489 A JP 18105489A JP 2808685 B2 JP2808685 B2 JP 2808685B2
Authority
JP
Japan
Prior art keywords
lead
antimony
electrolytic solution
storage 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 - Lifetime
Application number
JP1181054A
Other languages
Japanese (ja)
Other versions
JPH0346768A (en
Inventor
宣行 高見
直人 星原
康彦 鈴井
勝弘 高橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Priority to JP1181054A priority Critical patent/JP2808685B2/en
Publication of JPH0346768A publication Critical patent/JPH0346768A/en
Application granted granted Critical
Publication of JP2808685B2 publication Critical patent/JP2808685B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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

Landscapes

  • Cell Electrode Carriers And Collectors (AREA)
  • Secondary Cells (AREA)

Description

【発明の詳細な説明】 産業上の利用分野 本発明は、自動車用，民生機器用，産業用に広く用い
られている鉛蓄電池に関するもので、自己放電特性、過
放電放置後の充電受入性を改善するものである。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lead storage battery widely used for automobiles, consumer electronics, and industry, and has a self-discharge characteristic and a charge acceptability after being left in an over-discharge state. It will improve.

従来の技術 今般、自動車用鉛蓄電池は管理不要のメンテナンスフ
リー化が要求され、電池用格子材料として鉛−カルシウ
ム系合金が実用化されている、又、近年カーエレクトロ
ニクスの著しい発展により電池に関する負荷が増大し、
エンジンルームの高密度化により電池が高温状態で使用
され非常に過酷な条件で使用される機会が増えている。
メンテナンスフリー性能を維持し高温、高負荷での寿命
特性の改善として、格子表面にアンチモンを多く有する
層を形成させるなどの手段が使われている。2. Description of the Related Art In recent years, lead-acid batteries for automobiles have been required to be maintenance-free, requiring no management, and lead-calcium alloys have been put to practical use as battery grid materials. Increase,
Due to the high density of the engine room, the battery is used in a high temperature state, and the chance of using the battery under extremely severe conditions is increasing.
In order to maintain the maintenance-free performance and improve the life characteristics under high temperature and high load, means such as forming a layer having a large amount of antimony on the lattice surface is used.

一方、鉛蓄電池は、長期放置または過放電状態で放置
されると、充電不能となることが多く、使用不能とな
る。On the other hand, if the lead storage battery is left for a long time or left in an overdischarged state, it is often impossible to charge the battery and becomes unusable.

こうした欠点を改善する方法として、従来過放電後の
充填受入れ性能に効果がある、すずを格子合金中に添加
あるいは、表面にコーティングしたり、電解液中にリン
酸や、アルカリ金属イオンを添加する方法がある。As a method of improving such disadvantages, tin is conventionally effective in filling and receiving performance after overdischarge, and tin is added to the lattice alloy or coated on the surface, or phosphoric acid or an alkali metal ion is added to the electrolytic solution. There is a way.

発明が解決しようとする課題 過放電放置後、または長期放置により格子活物質界面
に絶縁層が形成される。このため格子一活物質界面に充
電電流が流れにくくなり、充電不能となる。この欠点を
改善する方法として格子合金中または、表面にすずを添
加する方法があるが、高温、高負荷寿命特性の改善には
ほとんど効果がない。Problems to be Solved by the Invention An insulating layer is formed at an interface of a lattice active material after being left for overdischarge or after being left for a long time. For this reason, it becomes difficult for a charging current to flow at the lattice-active material interface, and charging becomes impossible. As a method of improving this defect, there is a method of adding tin to the lattice alloy or to the surface, but it has almost no effect on improving the high temperature and high load life characteristics.

又、電解液中へのりん酸添加は、初期容量が低下し、
自己放電は大きなる。さらに、電解液中へのアルカリ金
属添加は、過放電放置された電解液の電動性を向上させ
る働きがあり、充填特性を向上させる働きがある。Also, the addition of phosphoric acid to the electrolyte reduces the initial capacity,
Self-discharge is large. Further, the addition of an alkali metal to the electrolytic solution has a function of improving the motorability of the electrolytic solution left overdischarged and a function of improving the filling characteristics.

しかし、長期放置，過放電放置後に生成する絶縁皮膜
に対しては、あまり効果がない。However, it has little effect on an insulating film formed after being left for a long period of time or overdischarged.

本発明は、上記従来の問題点を解決するもので優れた
メンテナンスフリー性、高温、深い放電での寿命特性を
維持しつつ、自己放電特性，過放電放置後の充電受入性
を改善するものである。The present invention solves the above-mentioned conventional problems and improves self-discharge characteristics and charge acceptability after being left in over-discharge while maintaining excellent maintenance-free properties and high-temperature, deep discharge life characteristics. is there.

課題を解決するための手段 この目的を達成するために本発明は、アンチモンを含
まない鉛−カルシウム系合金の表面にアンチモンを多く
含んだ層を有する電極を用い、かつ電解液中にアルカリ
金属イオンと、アルカリ土類イオンの少なくとも一方を
存在させるものである。Means for Solving the Problems In order to achieve this object, the present invention uses an electrode having a layer containing a large amount of antimony on the surface of a lead-calcium-based alloy containing no antimony, and contains an alkali metal ion in an electrolytic solution. And at least one of alkaline earth ions.

電極表面のアンチモンを多く含んだ層は、鉛−アンチ
モン、または鉛−アンチモン−すず合金薄膜を、鉛−カ
ルシウム系合金上に付与させたものである。The layer containing a large amount of antimony on the electrode surface is obtained by applying a lead-antimony or lead-antimony-tin alloy thin film on a lead-calcium alloy.

作用 この構成により、優れたメンテナンスフリー性、高
温、深い放電での寿命特性を維持しつつ、自己放電特
性、過放電後の充電受入性を改善することができる。Action With this configuration, it is possible to improve the self-discharge characteristics and the charge acceptability after overdischarge while maintaining excellent maintenance-free properties and life characteristics at high temperature and deep discharge.

実施例 以下本発明の一実施例について、図面を参照にしなが
ら説明する。Embodiment An embodiment of the present invention will be described below with reference to the drawings.

鉛−カルシムウ合金表面に鉛−5wt％アンチモン合金
薄膜を付与して格子体としたもの鉛−5wt％アンチモン
−5wt％すず合金薄膜を付与して格子体としたもの、比
較のために鉛−カルシウム合金を格子体としたものを正
極格子とし、酸化鉛，硫酸，水を混合したペースとを充
填し、正極板として、負極板とセパレーターをくみあわ
せ、12V,5時間率で48Ahの電池を作成した。また、アル
カリ金属イオンとして、Na+、アルカリ土類金属イオン
としてMg2+イオンを電解液中に添加した。この電池を9.
6Aで５時間定電流放電したのち常温で１カ月放置した。
放置後これらの電池を14.8V定電圧充電を行いその時の
充電電流を測定した。A lattice formed by applying a lead-5 wt% antimony alloy thin film to the surface of a lead-calcium alloy to form a lattice formed by applying a lead-5 wt% antimony-5 wt% tin alloy thin film, and lead-calcium for comparison A grid made of an alloy is used as a positive grid, filled with a pace mixed with lead oxide, sulfuric acid, and water, and a negative plate and a separator are combined as a positive plate to create a 48Ah battery at 12V, 5 hours rate did. Further, Na + as an alkali metal ion and Mg 2+ ion as an alkaline earth metal ion were added to the electrolytic solution. Replace this battery with 9.
After discharging at a constant current of 6 A for 5 hours, it was left at normal temperature for 1 month.
After standing, these batteries were charged at a constant voltage of 14.8 V, and the charging current at that time was measured.

第１図は、9.6Aで５時間定電流放電したのち常温で１
カ月放置し、放電後の電池を14.8Vで定電圧充電を行い
その時の10秒目,30秒目,60秒目充電電流値を示したもの
である、1,2,3は鉛−カルシウム合金で、１は電解液に
無添加、２は電解液中にNa+を加したもの、３は電解液
中にMg2+を添加したものである。4,5,6は鉛−カルシウ
ム合金表面に鉛−5wt％アンチモン合金薄膜を付与して
格子体としたもので、４は電解液に無添加、５は電解液
中にNa+を添加したもの、６は電解液中にMg2+を添加し
たものである。7,8,9は5wt％アンチモン−5wt％すず合
金薄膜を付与して格子体としたもので、７は電解液に無
添加、８は電解液中にNa+を添加したもの、９は電解液
中にMg2+を添加したものである。電極表面にアンチモン
を付与し、アルカリ金属イオン，アルカリ土類金属イオ
ン添加したものの、30秒目電流は、表面にアンチモンを
付与していないものに比較して約２倍、電極表面にアン
チモン−すずを付与し、アルカリ金属イオン，アルカリ
土類金属イオンを添加したものは、電極表面にアンチモ
ンを付与し、アルカリ金属イオン，アルカリ土類金属イ
オン添加したものにくらべて30秒目充電電流は、やや向
上した程度である。Fig. 1 shows that after discharging at a constant current of 9.6 A for 5 hours,
After leaving for a month, the discharged battery was charged at a constant voltage of 14.8 V, and the charge current values at the 10th, 30th, and 60th seconds were shown at that time. 1, 2, and 3 are lead-calcium alloys. 1 is no addition to the electrolyte, 2 is Na + added to the electrolyte, and 3 is Mg 2+ added to the electrolyte. 4, 5 and 6 are lead-calcium alloy surfaces with a lead-5wt% antimony alloy thin film applied to form a lattice, 4 is no addition to the electrolyte, 5 is Na + added to the electrolyte , 6 are those obtained by adding Mg 2+ to the electrolytic solution. 7, 8 and 9 are grids formed by applying a 5 wt% antimony-5 wt% tin alloy thin film, 7 is not added to the electrolytic solution, 8 is Na + added to the electrolytic solution, 9 is the electrolytic solution. Mg 2+ was added to the solution. Although antimony was applied to the electrode surface and alkali metal ions and alkaline earth metal ions were added, the current at the 30th second was about twice as large as that without antimony applied to the surface. And the addition of alkali metal ions and alkaline earth metal ions gives antimony to the electrode surface, and the charging current in the 30th second is slightly higher than that obtained by adding alkali metal ions and alkaline earth metal ions. To the extent improved.

このように、鉛−アンチモンまたは、鉛−アンチモン
−すずを格子表面に付与し、電解液中にNa+、Mg2+添加
することにより相乗効果があり、充電電流、充電受入性
が改善された。As described above, by adding lead-antimony or lead-antimony-tin to the lattice surface and adding Na + and Mg 2+ to the electrolytic solution, a synergistic effect was obtained, and the charging current and charge acceptability were improved. .

発明の効果 以上のように、本発明では優れたメンテナンスフリー
性、高温、深い放電での寿命特性を維持しつつ、自己放
電特性、過放電放置後の充電受入性を改善することがで
き、その工業的価値は非常に大きい。As described above, the present invention can improve the self-discharge characteristic and the charge acceptability after being left over-discharge while maintaining the excellent maintenance-free property, high temperature, and the life characteristics in deep discharge. The industrial value is very large.

【図面の簡単な説明】[Brief description of the drawings]

第１図は、過放電放置後の充電受入性の比較曲線を示す
特性図である。FIG. 1 is a characteristic diagram showing a comparison curve of charge acceptability after overdischarge standing.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 高橋 勝弘 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 昭64−6374（ＪＰ，Ａ) 特開 昭63−213263（ＪＰ，Ａ) 特開 昭59−29383（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 10/06 - 10/12──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Katsuhiro Takahashi 1006 Kadoma, Kadoma, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (56) References JP-A-64-6374 (JP, A) JP-A-63- 213263 (JP, A) JP-A-59-29383 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) H01M 10/06-10/12

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】アンチモンを含まない鉛−カルシウム系合
金の表面にアンチモンを多く含んだ層を有する電極を用
い、かつ電解液中にアルカリ金属イオンと、アルカリ土
類イオンの少なくとも一方を含むことを特徴とした鉛蓄
電池。An electrode having a layer containing a large amount of antimony on a surface of a lead-calcium-based alloy containing no antimony, and containing at least one of an alkali metal ion and an alkaline earth ion in an electrolytic solution. Lead-acid battery with features. 【請求項２】前記の電極表面のアンチモンを多く含んだ
層は、鉛−アンチモン、または鉛−アンチモン−すず合
金であることを特徴とした特許請求の範囲１項記載の鉛
蓄電池。2. The lead-acid battery according to claim 1, wherein the layer containing a large amount of antimony on the electrode surface is made of lead-antimony or a lead-antimony-tin alloy.
JP1181054A 1989-07-13 1989-07-13 Lead storage battery Expired - Lifetime JP2808685B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1181054A JP2808685B2 (en) 1989-07-13 1989-07-13 Lead storage battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1181054A JP2808685B2 (en) 1989-07-13 1989-07-13 Lead storage battery

Publications (2)

Publication Number Publication Date
JPH0346768A JPH0346768A (en) 1991-02-28
JP2808685B2 true JP2808685B2 (en) 1998-10-08

Family

ID=16093972

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1181054A Expired - Lifetime JP2808685B2 (en) 1989-07-13 1989-07-13 Lead storage battery

Country Status (1)

Country Link
JP (1) JP2808685B2 (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5929383A (en) * 1982-08-12 1984-02-16 Shin Kobe Electric Mach Co Ltd Sealed lead storage battery
JPS63213263A (en) * 1987-02-27 1988-09-06 Shin Kobe Electric Mach Co Ltd Lead storage battery
JPS646374A (en) * 1987-06-29 1989-01-10 Matsushita Electric Ind Co Ltd Lead storage battery

Also Published As

Publication number Publication date
JPH0346768A (en) 1991-02-28

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