JPS61161660A - Lead-acid battery - Google Patents

Lead-acid battery

Info

Publication number
JPS61161660A
JPS61161660A JP60001601A JP160185A JPS61161660A JP S61161660 A JPS61161660 A JP S61161660A JP 60001601 A JP60001601 A JP 60001601A JP 160185 A JP160185 A JP 160185A JP S61161660 A JPS61161660 A JP S61161660A
Authority
JP
Japan
Prior art keywords
lead
battery
tin
oxide
grid
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
Application number
JP60001601A
Other languages
Japanese (ja)
Inventor
Hiroshi Yasuda
博 安田
Naoto Hoshihara
直人 星原
Teruaki Ishii
輝秋 石井
Katsuhiro Takahashi
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
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Priority to JP60001601A priority Critical patent/JPS61161660A/en
Publication of JPS61161660A publication Critical patent/JPS61161660A/en
Pending legal-status Critical Current

Links

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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
    • H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
    • 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)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

PURPOSE:To increase deep charge-discharge life by adding a specified compound to a positive active material of a battery in which non-antimony alloy is used in a positive grid. CONSTITUTION:Lead oxide powder, dilute sulfuric acid, water, and tin powder are mixed, and stirred to make paste. The paste is filled in a lead-calcium-tin alloy grid, and dried and aged to form a positive electrode of lead-acid battery. In drying and aging processes, metallic lead in lead oxide and tin are converted into lead oxide, and tin oxide, and complex oxide of lead and tin. A battery for automobile was fabricated with this electrode plate A as usual and charge- discharge cycle test was conducted. The battery using the plate A showed five time longer cycle life compared with a battery using conventional plate B, because formation of dense lead sulfate layer between the grid and active material is suppressed.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は、自動車やその他の用途に使用される鉛蓄電池
の改良に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to improvements in lead acid batteries used in automobiles and other applications.

従来の技術 最近、鉛蓄電池用格子体合金として電池の減液特性にす
ぐれ、かつ自己放電特性にもすぐれた鉛−カルシウム合
金系が、従来より普及していた鉛−アンチモン系合金に
かわり広く用いられるようになってきた。Background of the Invention Recently, lead-calcium alloys have been widely used as lattice alloys for lead-acid batteries in place of the conventionally popular lead-antimony alloys, which have excellent liquid reduction properties and self-discharge properties. It has become possible to do so.

発明が解決しようとする問題点 しかしこのようｌ鉛−カルシウム系合金製の格子体を用
いる電池は、深い充放電がくりかえされたとき、正極格
子と活物質との界面に高抵抗物質を生成し、電池容量が
急激に低下しやすいという問題がめった。Problems to be Solved by the Invention However, in batteries using such lead-calcium alloy grids, when deep charging and discharging are repeated, high-resistance substances are generated at the interface between the positive electrode grid and the active material. However, there was a problem that the battery capacity tended to decrease rapidly.

本発明は、このような問題点を解決することを目的とし
たものである。The present invention aims to solve these problems.

問題点を解決するための手段 すなわち本発明は上記の目的達成のため正極格子に鉛−
カルシウム系合金を用いた電池の正極活物質中にスズ化
合物を添加したものである。Means for solving the problem, that is, the present invention is to achieve the above object by adding lead to the positive electrode grid.
A tin compound is added to the positive electrode active material of a battery using a calcium-based alloy.

作用 鉛−カルシウム系合金等の非アンチモン系合金を正極格
子に用いる電池では、深い充放電で格子と活物質との界
面に形成される高抵抗物質は硫酸鉛と思われる。これは
鉛−アンチモン系合金を用いた場合、正極活物質と格子
との界面中にα−Ｐｂ０２が多く含まれるのに対し、鉛
−カルシウム系合金ではβ−Ｐｂ０２のみがほとんど生
成するためと考えられる。β−Ｐｂ０２はα−ＰｂＯｚ
ｆ／ｉｃ＜らべて反応性に富み、放電反応によりすみや
かに硫酸鉛が生成する。これが鉛−カルシウム系合金で
深い充放電をくりかえしたときの容量低下の原因である
。In batteries in which a non-antimony alloy such as a lead-calcium alloy is used for the positive electrode grid, the high resistance substance formed at the interface between the grid and the active material during deep charging and discharging is thought to be lead sulfate. This is thought to be because when a lead-antimony alloy is used, a large amount of α-Pb02 is contained in the interface between the positive electrode active material and the lattice, whereas with a lead-calcium alloy, almost only β-Pb02 is generated. It will be done. β-Pb02 is α-PbOz
It is highly reactive compared to f/ic, and lead sulfate is quickly produced by the discharge reaction. This is the cause of the capacity drop when lead-calcium alloys are repeatedly deeply charged and discharged.

本発明者らは正極活物質中にスズ化合物を添加すると、
格子と活物質との間に生成するち密な硫酸鉛層を抑制で
きることを見いだした。When the present inventors added a tin compound to the positive electrode active material,
It was discovered that the dense lead sulfate layer that forms between the lattice and the active material can be suppressed.

実施例 以下実施例により本発明を説明する。Example The present invention will be explained below with reference to Examples.

鉛蓄電池正極活物質は通常鉛酸化物粉末（金属鉛的２０
％　、残鉛酸化物）、稀硫酸と水を攪拌しペースト状と
したものを鉛合金格子に塗りつけて乾燥、熟成工程によ
り固化させたのち、これを電解酸化して二酸化鉛とする
ことにより作られる。Lead-acid battery cathode active material is usually lead oxide powder (metal lead 20
%, residual lead oxide), dilute sulfuric acid and water are stirred to form a paste, which is applied to a lead alloy grid, dried and solidified through an aging process, and then electrolytically oxidized to produce lead dioxide. It will be done.

本実施例では鉛酸化物粉末１ｋｑに対し、濃度４０　ｗ
ｔ　俤の硫酸１００ＣＣ１水１０００Ｃそれにスズ粉末
（粒径１〜１０μ）を６ｏｊｉ加え、攪拌してペースト
状としたのち、鉛−力ｌレシウムースズ合金（Ｃ＆　０
．０６ｗｔ％、　ｓｎ　Ｏ，５ｗｔ％　）の格子体に充
填したのち上記方法により６０’Ｃ温度下で乾燥、熟成
を行なった。乾燥、熟成工程の中で鉛酸化物中の金属鉛
およびスズは酸化されてそれぞれ酸化鉛およびスズ酸化
物およびそれらの複合酸化物となる。In this example, the concentration was 40 W for 1 kq of lead oxide powder.
To 100 C of sulfuric acid, 1000 C of water, add 6 oji of tin powder (particle size 1 to 10 μm), stir to form a paste, and prepare a lead-resium tin alloy (C&0
．． 06 wt%, snO, 5 wt%), and then dried and aged at a temperature of 60'C according to the above method. During the drying and aging process, the metal lead and tin in the lead oxide are oxidized to become lead oxide and tin oxide, and their composite oxides, respectively.

また比較例としてスズ粉末を加えない外は前記と同一工
程により極板を製作した。Further, as a comparative example, an electrode plate was manufactured by the same process as above except that tin powder was not added.

この本実施例人と比較例Ｂの極板を用いて常法により自
動車用電池を組立て、化成を行なった。Using the electrode plates of this Example and Comparative Example B, an automobile battery was assembled and chemically formed by a conventional method.

なお電池は１２Ｖ仕様の５５Ｄ２３形自動車用電池とし
た。The battery used was a 55D23 type automobile battery with a 12V specification.

これらの電池を９．６人で終止電圧１０．５Ｖまで放電
し、さらに９．６人で放電量の１２ｏ％充電するのを−
サイクルとするサイクル寿命試験を行なった。その結果
を図に示すが、本発明による電池ムでは従来電池Ｂにく
らべ倍以上の寿命を有することがわかる。It took 9.6 people to discharge these batteries to a final voltage of 10.5V, and then another 9.6 people to charge them to 12% of the discharge amount.
A cycle life test was conducted. The results are shown in the figure, and it can be seen that the battery according to the present invention has a lifespan more than double that of the conventional battery B.

発明の効果 以上の通り本発明は鉛−カルシウム系合金を正極格子に
用いた電池の深い充放電サイクル寿命を向上するもので
ある。Effects of the Invention As described above, the present invention improves the deep charge/discharge cycle life of a battery using a lead-calcium alloy in the positive electrode grid.

このような本発明により、鉛−カルシウム系合金でもサ
イクル用途など多岐分野に使用することが可能となる。According to the present invention, even lead-calcium alloys can be used in a wide variety of fields such as cycle applications.

【図面の簡単な説明】[Brief explanation of the drawing]

図は本発明の電池と従来電池のサイクル寿命試験結果を
示す図である。 代理人の氏名　弁理士　中　尾　敏　男　ほか１名ア　
イ　７１１．’ＩＫ＜回ノThe figure shows the cycle life test results of the battery of the present invention and the conventional battery. Name of agent: Patent attorney Toshio Nakao and one other person
I 711. 'IK< times no

Claims (1)

【特許請求の範囲】[Claims] 鉛−カルシウム系合金からなる正極格子を用いた鉛蓄電
池であって、前記格子に充填する正極活物質中にスズ化
合物を添加したことを特徴とする鉛蓄電池。1. A lead-acid battery using a positive electrode grid made of a lead-calcium alloy, characterized in that a tin compound is added to a positive electrode active material filled in the grid.
JP60001601A 1985-01-09 1985-01-09 Lead-acid battery Pending JPS61161660A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60001601A JPS61161660A (en) 1985-01-09 1985-01-09 Lead-acid battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60001601A JPS61161660A (en) 1985-01-09 1985-01-09 Lead-acid battery

Publications (1)

Publication Number Publication Date
JPS61161660A true JPS61161660A (en) 1986-07-22

Family

ID=11506017

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60001601A Pending JPS61161660A (en) 1985-01-09 1985-01-09 Lead-acid battery

Country Status (1)

Country Link
JP (1) JPS61161660A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012043556A1 (en) * 2010-09-29 2012-04-05 株式会社Ｇｓユアサ Lead storage battery and idling stop vehicle using same
JP2015191691A (en) * 2014-03-27 2015-11-02 株式会社Ｇｓユアサ Lead storage battery, and positive electrode plate thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53118742A (en) * 1977-03-25 1978-10-17 Japan Storage Battery Co Ltd Maintenance free type lead storage battery

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53118742A (en) * 1977-03-25 1978-10-17 Japan Storage Battery Co Ltd Maintenance free type lead storage battery

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012043556A1 (en) * 2010-09-29 2012-04-05 株式会社Ｇｓユアサ Lead storage battery and idling stop vehicle using same
JP5748182B2 (en) * 2010-09-29 2015-07-15 株式会社Ｇｓユアサ Lead acid battery and idling stop vehicle using the same
JP2015167142A (en) * 2010-09-29 2015-09-24 株式会社Ｇｓユアサ Lead storage battery, and idling stop vehicle using same
JP2016225302A (en) * 2010-09-29 2016-12-28 株式会社Ｇｓユアサ Lead acid storage battery and idling stop vehicle using the same
JP2015191691A (en) * 2014-03-27 2015-11-02 株式会社Ｇｓユアサ Lead storage battery, and positive electrode plate thereof

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