KR20060062376A - Positive grid of lead-acid battery and an alloy therefor - Google Patents

Positive grid of lead-acid battery and an alloy therefor Download PDF

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KR20060062376A
KR20060062376A KR1020040101196A KR20040101196A KR20060062376A KR 20060062376 A KR20060062376 A KR 20060062376A KR 1020040101196 A KR1020040101196 A KR 1020040101196A KR 20040101196 A KR20040101196 A KR 20040101196A KR 20060062376 A KR20060062376 A KR 20060062376A
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grid
weight
alloy
lead
acid battery
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KR1020040101196A
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KR100692273B1 (en
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유재욱
윤강현
신태호
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주식회사 아트라스비엑스
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    • 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
    • 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
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
    • 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
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H01M4/745—Expanded metal
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

본 발명은 납축전지 포지티브 그리드 납합금과 이를 이용하여 제조된 그리드에 관한 것으로, 자세하게는 기계적 강도 및 내부식성 향상을 목적으로 하는 상대농도 0.05중량%∼0.07중량%의 Ca, 0.9중량%∼1.5중량%의 Sn, 0.007중량%~0.009중량의 Al, 0.02중량%∼0.04중량%의 Ba을 함유하는 납축전지의 포지티브 그리드 납합금과 이를 이용해서 제조된 그리드를 제공하기 위한 것이다. The present invention relates to a lead acid battery positive grid lead alloy and a grid manufactured using the same, and in particular, a relative concentration of 0.05 wt% to 0.07 wt% Ca, 0.9 wt% to 1.5 wt%, for the purpose of improving mechanical strength and corrosion resistance. A positive grid lead alloy of a lead acid battery containing% Sn, 0.007 wt% to 0.009 wt% Al, and 0.02 wt% to 0.04 wt% Ba, and a grid prepared using the same.

납축전지, 그리드 합금, 바륨, 주조 그리드, 익스펜드 그리드Lead Acid Battery, Grid Alloy, Barium, Foundry Grid, Expanded Grid

Description

납축전지의 포지티브 그리드와 그 제조용 납합금{Positive grid of Lead-acid battery and an alloy therefor} Positive grid of lead-acid battery and lead alloy for manufacturing thereof

본 발명은 납축전지 포지티브 그리드 납합금과 이를 이용하여 제조된 그리드에 관한 것으로, 자세하게는 기계적 강도 및 내부식성 향상을 목적으로 하는 상대농도 0.05중량%∼0.07중량%의 Ca, 0.9중량%∼1.5중량%의 Sn, 0.007중량% ~0.009중량%의 Al, 0.02중량%∼0.04중량%의 Ba을 함유하는 납축전지 포지티브 그리드 납합금과 이를 이용한 그리드를 제공하기 위한 것이다. The present invention relates to a lead acid battery positive grid lead alloy and a grid manufactured using the same, and in particular, a relative concentration of 0.05 wt% to 0.07 wt% Ca, 0.9 wt% to 1.5 wt%, for the purpose of improving mechanical strength and corrosion resistance. A lead acid battery positive grid lead alloy containing% Sn, 0.007% to 0.009% by weight of Al, and 0.02% to 0.04% by weight of Ba, and a grid using the same.

납축전지용 포지티브 그리드 합금으로는 Pb-Ca-Sn계 합금을 사용해 왔으나. 최근의 가혹한 사용환경(고온 및 과충전 현상)은 그리드의 부식이나 그로스 변형을 일으켜 조기에 수명이 종지 되는 일이 있다. 그리하여 그리드의 내부식성 및 기계적 강도 개선이 요구되고 있다. Pb-Ca-Sn based alloys have been used as the positive grid alloy for lead acid batteries. Recent harsh use environments (high temperature and overcharge phenomena) may lead to corrosion of the grid or gross deformation, leading to premature end of life. Thus, there is a need to improve the corrosion resistance and mechanical strength of the grid.

이러한 개선방향으로, USP4233070, USP4358518은 고함량 Ba를 첨가하여 기계적 강도 및 내식성을 향상시킨 납축전지 그리드 합금을 개시하였고, WO9730183은 0.05~0.12중량% Ca, 3중량% 이하의 Sn, 0.002~0.04중량% Al, 0.02중량% 이하의 Ba 그리드합금으로 경화속도 증대 및 시간에 따른 기계적 성질을 유지하는 납축전지용 그리드 합금을 개시하고, WO3088385는 0.02~0.05중량% Ca, 0.04~2.5중량% Sn, 0.005~0.04중량% Al, 0.002중량% 미만의 Ba 그리드 합금으로 내부식성과 기계적 강도가 향상된 납축전지용 그리드 합금을 제공한다.In this direction of improvement, USP4233070 and USP4358518 disclose a lead acid battery grid alloy in which high content of Ba is added to improve mechanical strength and corrosion resistance, and WO9730183 has 0.05 to 0.12 wt% Ca, 3 wt% or less Sn, and 0.002 to 0.04 wt%. Disclosed is a lead acid battery grid alloy which increases the curing rate and maintains mechanical properties over time with a Ba grid alloy of less than or equal to 0.0 Al by 0.02 wt%. WO3088385 discloses 0.02 to 0.05 wt% Ca, 0.04 to 2.5 wt% Sn, 0.005 Ba grid alloys of less than -0.04 wt% Al and less than 0.002 wt% provide grid alloys for lead acid batteries with improved corrosion resistance and mechanical strength.

자동차용 납축전지는 경량화 및 긴 수명을 필요로 하게 되며, 가혹한 조건에서의 충방전에 따른 부동태 전위를 높여 내식성 향상과 그로스 문제를 해결해야할 과제를 안고 있다. Automotive lead acid batteries require weight reduction and long service life, and have a problem of improving corrosion resistance and gross problems by increasing the passive potential due to charging and discharging under severe conditions.

본 발명에서는 구성합금의 초기강도를 향상시키고, 활물질 부착력 및 그리드 부식에 따른 그리드 그로스를 억제하기 위해 Pb-Ca-Sn-Ba 합금계의 조성범위를 변경함으로써 포지티브 그리드 합금으로의 사용에 따른 문제점을 최소화하여 그 목적을 달성하는 것을 그 기술적인 과제로 한다.
In the present invention, to improve the initial strength of the constituent alloy, and to change the composition range of the Pb-Ca-Sn-Ba alloy system in order to suppress the grid gross due to active material adhesion and grid corrosion to solve the problems caused by use as a positive grid alloy The technical task is to minimize and achieve the purpose.

본 발명은 납축전지 포지티브 그리드 납합금에 관한 것으로, 상대농도 0.05중량% 이상 0.07중량% 이하 Ca, 0.9중량% 이상 1.5중량% 이하 Sn, 0.007중량%이상 0.009중량%이하 Al 및 0.02중량%이상 0.04중량% 이하 Ba를 조성범위로 하는 납합금을 특징으로 한다.The present invention relates to a lead acid battery positive grid lead alloy, the relative concentration of 0.05% to 0.07% by weight Ca, 0.9% to 1.5% by weight Sn, 0.007% to 0.009% by weight Al and 0.02% to 0.04% It is characterized by a lead alloy having a composition percentage of Ba or less by weight.

본 발명은, 추가로, 위와 같은 조성물에 0.007중량% 이상 0.01중량% 이하의 은을 첨가한 합금을 제공한다. The present invention further provides an alloy in which 0.007% by weight or more and 0.01% by weight or less of silver is added to the above composition.

합금에 함유된 Ca는 합금의 기계적 강도를 높이며, 그 함량이 0.05중량% 미만에서는 기계적 강도가 불충분하게 되며, 0.07중량%이상에서는 내부식성을 저하시킬 우려가 있다.바람직한 Ca의 함유량은 0.05중량%이상에서 0.06중량%이하이다. Ca contained in the alloy increases the mechanical strength of the alloy, and if the content is less than 0.05% by weight, the mechanical strength is insufficient, and if it is more than 0.07% by weight, the corrosion resistance may be lowered. It is 0.06 weight% or less above.

Sn은 합금의 주조성과 기계적 강도를 향상시키며, 충방전시 그리드 표면에 생성되는 부동태피막의 생성속도를 감소시켜 전기전도성을 높이는 작용을 한다. Sn함량이 0.9중량%이하에서는 내식성이 저하될 우려가 있으며, 1.5중량%이상에서는 합금의 미세조직의 조대화로 인해 급격한 입계부식(粒界腐蝕)이 진행될 수 있다. 바람직한 Sn의 함량은 1.0중량% 이상 1.3중량% 이하이다. Sn improves the castability and mechanical strength of the alloy, and increases the electrical conductivity by reducing the formation rate of the passivation film formed on the grid surface during charging and discharging. If the Sn content is less than 0.9% by weight, the corrosion resistance may be lowered. If the Sn content is more than 1.5% by weight, rapid grain boundary corrosion may proceed due to coarsening of the microstructure of the alloy. Preferable content of Sn is 1.0 weight% or more and 1.3 weight% or less.

Ba는 합금의 기계적 강도를 증가시키는 작용을 하며, 0.02중량% 이상 0.04중량% 이하의 함량을 유지시킴으로써 강도와 내식성을 향상시킬 수 있다. 바람직한 Ba함량은 0.02중량%이상 0.03중량%이하이다.Ba serves to increase the mechanical strength of the alloy, it is possible to improve the strength and corrosion resistance by maintaining a content of 0.02% by weight or more and 0.04% by weight or less. Preferable Ba content is 0.02 weight% or more and 0.03 weight% or less.

Ba의 첨가는 주조 후 그리드 합금의 경화속도를 증가시키고 결과적으로는 합금의 최대경도를 향상시킴으로써 페이스팅 공정을 위해 필요한 최소 경도에 더욱 빨리 도달하는 것을 가능하게 된다.The addition of Ba makes it possible to reach the minimum hardness required for the pasting process faster by increasing the cure rate of the grid alloy after casting and consequently improving the maximum hardness of the alloy.

Ca와 Sn의 중량함량비를 12이상(Sn/Ca>12)으로 하고, 이에 Ba를 첨가함으로써, 기계적 강도를 부여해 별도의 그리드 열처리 없이 핸들링이 가능하게 하며, Sn의 편석(Segregation)없는 균일한 분산 및 조직 미세화를 통해 내부식성 향상 및 크리프(Creep) 성질을 향상시킬 수 있는 납축전지용 합금을 제공한다.Ca and Sn content ratio of 12 or more (Sn / Ca> 12), and by adding Ba to it, mechanical strength is given to enable handling without additional grid heat treatment, and uniform segregation without segregation. It provides an alloy for lead-acid batteries that can improve corrosion resistance and creep properties through dispersion and microstructure.

은(Ag)은 0.007중량% 이상 0.01중량%이하에서 합금의 기계적 강도를 증가시켜 고온 내구성을 향상시키며, 심방전 회복 특성을 향상시킨다.Silver (Ag) increases the mechanical strength of the alloy at 0.007% by weight or more and 0.01% by weight or less to improve high temperature durability and improve deep discharge recovery characteristics.

이와 같은 본 발명의 합금은 이로써 주조하여 주조된 형태 또는 압연공정으로 익스펜드(expand) 형태를 이루도록 납축전지용 포지티브 그리드를 형성시킨다. The alloy of the present invention thereby forms a positive grid for lead-acid batteries to form an expanded form by casting and casting or a rolling process.

그리고, 본 발명의 합금으로 주조하는 그리드는 이를 주조 후 열처리 없이 사용할 수 있다.And, the grid cast with the alloy of the present invention can be used without heat treatment after casting it.

이와 같은 본 발명은 구성합금의 초기강도를 향상시키고, 활물질 부착력 및 그리드 부식에 따른 그리드 그로스를 억제하여 포지티브 그리드 합금으로의 사용에 따른 문제점을 최소화할 수 있는 효과가 있다.







The present invention improves the initial strength of the constituent alloy, and has the effect of minimizing the problems caused by use as a positive grid alloy by suppressing the grid gross due to the adhesion of the active material and the grid corrosion.







Claims (6)

상대농도 0.05중량%∼0.07중량%의 칼슘, 상대농도 0.9중량%∼1.5중량%의 주석, 상대농도 0.007중량%∼0.009중량%의 알루미늄, 상대농도 0.02중량%∼0.04중량%의 바륨을 함유하는 납축전지용 납합금.Containing 0.05% to 0.07% by weight of calcium, tin of 0.9% to 1.5% by weight of tin, aluminum of 0.007% to 0.009% by weight of relative concentration, and barium of 0.02% to 0.04% by weight of relative Lead alloys for lead acid batteries. 제 1항에 있어서, 상기 합금에 0.007중량% 이상 0.01중량% 이하의 은이 첨가된 것을 특징으로 하는 납축전지용 납합금.The lead alloy for lead acid battery according to claim 1, wherein 0.007% by weight or more and 0.01% by weight or less of silver is added to the alloy. 상대농도 0.05중량%∼0.07중량%의 칼슘, 상대농도 0.9중량%∼1.5중량%의 주석, 상대농도 0.007중량%∼0.009중량%의 알루미늄, 상대농도 0.02중량%∼0.04중량%의 바륨을 함유하는 납합금으로 제조된 것을 특징으로 하는 납축전지용 포지티브 그리드.Containing 0.05% to 0.07% by weight of calcium, tin of 0.9% to 1.5% by weight of tin, aluminum of 0.007% to 0.009% by weight of relative concentration, and barium of 0.02% to 0.04% by weight of relative Positive grid for lead acid battery, characterized in that made of lead alloy. 제3항에 있어서, 상기 합금에 0.007중량% 이상 0.01중량% 이하의 은이 첨가된 것을 특징으로 하는 납축전지용 포지티브 그리드4. The positive grid for lead acid battery according to claim 3, wherein 0.007% by weight or more and 0.01% by weight or less of silver is added to the alloy. 제3항 또는 제4항에 있어서, 그리드가 주조된 형태를 가짐을 특징으로 하는 납축전지용 포지티브 그리드The positive grid for lead acid battery according to claim 3 or 4, wherein the grid has a cast shape. 제3항 또는 제4항에 있어서, 그리드가 익스펜드된 형태를 가짐을 특징으로 하는 납축전지용 포지티브 그리드The positive grid of a lead acid battery according to claim 3 or 4, wherein the grid has an expanded form.
KR1020040101196A 2004-12-03 2004-12-03 Positive grid of Lead-acid battery and an alloy therefor KR100692273B1 (en)

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Publication number Priority date Publication date Assignee Title
FR2745009B1 (en) 1996-02-16 1998-05-07 Metaleurop Sa LEAD-CALCIUM ALLOYS, ESPECIALLY FOR BATTERY GRIDS
JP2002329499A (en) 2001-04-27 2002-11-15 Furukawa Battery Co Ltd:The Lead-based alloy for lead storage battery
US20020182500A1 (en) 2001-06-04 2002-12-05 Enertec Mexico, S. De R.L. De C.V. Silver-barium lead alloy for lead-acid battery grids

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