JPH01143148A - Lattice body for lead storage battery - Google Patents

Lattice body for lead storage battery

Info

Publication number
JPH01143148A
JPH01143148A JP62299140A JP29914087A JPH01143148A JP H01143148 A JPH01143148 A JP H01143148A JP 62299140 A JP62299140 A JP 62299140A JP 29914087 A JP29914087 A JP 29914087A JP H01143148 A JPH01143148 A JP H01143148A
Authority
JP
Japan
Prior art keywords
alloy
lead
lattice body
addition
charge recovery
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
Application number
JP62299140A
Other languages
Japanese (ja)
Other versions
JPH07118320B2 (en
Inventor
Imakichi Hirasawa
今吉 平沢
Ryosuke Morinari
森成 良佐
Shoji Shimizu
祥司 清水
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.)
Resonac Corp
Original Assignee
Shin Kobe Electric Machinery 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 Shin Kobe Electric Machinery Co Ltd filed Critical Shin Kobe Electric Machinery Co Ltd
Priority to JP62299140A priority Critical patent/JPH07118320B2/en
Publication of JPH01143148A publication Critical patent/JPH01143148A/en
Publication of JPH07118320B2 publication Critical patent/JPH07118320B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/68Selection of materials for use in lead-acid accumulators
    • H01M4/685Lead alloys
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

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

Abstract

PURPOSE:To improve the charge recovery performance after over-discharging a battery and leaving it intact by covering a lead-tin alloy added with the specific ratio quantity of tin to high-purity lead on part of the surface of a lattice body made of a lead-calcium-tin alloy. CONSTITUTION:A Pb-Sb alloy added with Sn 0.01-0.2% to Pb with the purity of 99.99% or above is covered on part of the surface of a lattice body for positive electrode made of a Pb-Ca-Sn alloy. As a result, a resistance body PbOx generated on the interface between the lattice body and an active material can be made thin in thickness. When the addition of Sn is 0.01% or below, the adding effect has much dispersion, the adding effect is not so remarkable at 0.2-1.9%, and the efficiency of the addition is bad at 1.9% or above. The charge recovery performance after a battery is over-discharged and left intact can be thereby improved while the addition of Sn is kept to a trace quantity.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は鉛−カルシウム−錫(Pb −Ca−錫)合金
主体の鉛蓄電池用格子体に関するものである。
DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a lead-acid battery grid mainly composed of a lead-calcium-tin (Pb-Ca-tin) alloy.

従来の技術 陽極用格子体および陰極用格子体にPbCa−Sn合金
を用いる、いわゆるカルシウム電池(Ca電池)は自己
放電が少なく、減液量が少ないという点で、従来の電池
(陽極用格子体および陰極用格子体にpb−5l)合金
を用いたもの)あるいは/”1イブリツド電池(陽極用
格子体に円) −S +3今金)、陰極用格子体にpb
−PI) −Ca −Snn含金用いたもの)より優れ
ている。
Conventional technology So-called calcium batteries (Ca batteries) that use PbCa-Sn alloys for the anode grid and cathode grid have little self-discharge and less liquid loss, compared to conventional batteries (anode grid). and a battery using pb-5l) alloy for the cathode grid) or /”1 hybrid battery (circle for the anode grid), pb-5l alloy for the cathode grid
-PI) -Ca-Snn-containing metal).

しかし、Ca電池の最大の欠点は過放電放置後の充電回
復性が悪いということである。特に、Pb−Ca−5n
今金を用いることを前提にしているシール鉛電池では上
記欠点の解消は最重要課題である。また、自動車用鉛蓄
電池は、一部ハイブリッド電池という形でCa電池の欠
点を回避しているが、逆にそれに伴う自己放電特性の低
下、減液特性の低下は避けられない。
However, the biggest drawback of Ca batteries is that they have poor charge recovery properties after being left overdischarged. In particular, Pb-Ca-5n
Eliminating the above drawbacks is the most important issue for sealed lead batteries, which are based on the use of modern metal. Furthermore, although some of the lead-acid batteries for automobiles are in the form of hybrid batteries to avoid the drawbacks of Ca batteries, conversely, the accompanying deterioration in self-discharge characteristics and deterioration in liquid reduction characteristics cannot be avoided.

Ca電池の欠点である過放電放置後の充電回復性を向上
させる手段としては、従来、電解液中への硫酸ナトリウ
ム(Na2SO4)の添加、Pb−Ca−Sn合金中の
Sn量の増加などが知られている。前者の手段は、過放
電放置によって電解液中の硫酸(n2so、)が消費さ
れイオン伝導度が低下するのを防ぐものであり、後者の
手段は、過放電放置中格子体と活物質(PbO□)との
界面に生成するPbOxなる抵抗体の性質を変え充電性
を向上させるものである。格子体の合金であるl’b−
Ca  Sn合金中のSn量は一般に0.1〜1.0%
であるが、過放電放置後の充電回復性を向上させるため
には約2%以上の添加量が必要であると言われている。
Conventionally, methods to improve charge recovery after overdischarge, which is a drawback of Ca batteries, include adding sodium sulfate (Na2SO4) to the electrolyte and increasing the amount of Sn in the Pb-Ca-Sn alloy. Are known. The former means prevents sulfuric acid (NSO, This is to change the properties of the PbOx resistor produced at the interface with □) to improve charging performance. l'b-, which is an alloy of lattice bodies
The amount of Sn in CaSn alloy is generally 0.1-1.0%
However, it is said that an addition amount of about 2% or more is required to improve charge recovery after overdischarge.

発明が解決しようとする問題点 本発明は上記したCa電池の欠点である過放電放置後の
充電回復性を向上させることを目的としている。
Problems to be Solved by the Invention The purpose of the present invention is to improve the charge recovery performance after being left over-discharged, which is the drawback of the Ca battery described above.

問題点を解決するための手段 過放電放置後の充電回復性を向上させるため、本発明で
は、Pb −Ca −Sn合金より成る陽極用格子体の
表面の一部が、純度99.99%以上の1)旧こSnを
0.01〜0.2%添加したPb−5n今金で被覆され
たことを′vf徴としている。
Means for Solving the Problems In order to improve charge recovery after over-discharging and leaving, in the present invention, a part of the surface of the anode lattice made of a Pb-Ca-Sn alloy has a purity of 99.99% or more. 1) The coating with Pb-5n gold to which 0.01 to 0.2% of Sn was added is considered to be a 'vf feature.

作用 本発明の作用を第1図によって説明する。第1図はPb
−5n?f金と活物質(pbo□)との界面に生成する
PI)OXなる抵抗体の厚みをPb −Sn合金中のS
nの添加量との関係で示したものである。Pb  Sn
合金は純度99.99%以上のpbに純度99.999
9%のSnを添加して行くことによって調製した。また
、PIJO×なる抵抗体はPb−3n今金表面に活物質
の粉末を圧着した後一定の熱処理(60℃、24hr)
を行なうことによって生成させた。抵抗体の厚みの測定
はインピーダンスの複索平面解析および断面の走査型電
子顕微鏡(SEM)観察によった。抵抗体の厚みから、
Snの顕著な効果は0.05%付近および2%以上に見
られることがわかる。Snを2%以上添加したときの効
果については従来から言われているところであるが、こ
のように0.05%付近のSnの添加量でも同等の効果
のあることがわかる。以上のように、pb−Ca −S
n合金より成る陽極用格子体の表面を0.01〜0.2
%のSnを含む円)  Sn合金によって被覆すること
により格子体と活物質との界面に生成するPbOxなる
抵抗体の厚みを薄くすることができ、過放電放置後の充
電回復性を向上することができる。snの添加量は0.
01%以−ドでは添加効果にバラツキが多(、また、0
.2%〜1.9%では添加効果があまり顕著でなく 、
1.9以上では添加量の効率が悪い。
Function The function of the present invention will be explained with reference to FIG. Figure 1 shows Pb
-5n? f The thickness of the resistor called PI)OX generated at the interface between gold and the active material (pbo□) is
This is shown in relation to the amount of n added. Pb Sn
The alloy has a purity of 99.999% to PB with a purity of over 99.99%
It was prepared by adding 9% Sn. In addition, the PIJO× resistor is made by compressing the active material powder onto the Pb-3n metal surface and then subjecting it to a certain heat treatment (60°C, 24 hours).
It was generated by doing The thickness of the resistor was measured by a compound plane analysis of impedance and by scanning electron microscopy (SEM) observation of the cross section. From the thickness of the resistor,
It can be seen that the remarkable effect of Sn is seen at around 0.05% and at 2% or more. Although the effect of adding 2% or more of Sn has been said in the past, it can be seen that the same effect can be obtained even when the amount of Sn added is around 0.05%. As mentioned above, pb-Ca-S
The surface of the anode grid made of n alloy is 0.01 to 0.2
% of Sn) By coating with Sn alloy, the thickness of the PbOx resistor formed at the interface between the lattice and the active material can be reduced, and the charge recovery after overdischarge can be improved. Can be done. The amount of sn added is 0.
At 0.01% or higher, there is a lot of variation in the additive effect (and at 0.01% or higher,
.. The effect of addition is not very noticeable between 2% and 1.9%.
If it is 1.9 or more, the efficiency of addition is poor.

実施例 次に本発明の一実施例について述べる。Example Next, one embodiment of the present invention will be described.

純度99.99%以上のpbに3口を0.05%添加し
たpb−Sn合金を調製し、これを厚さ0.1ta+a
に圧延した。次に、厚さ5Il1mのPb −Ca −
Sn合金板と上記ph−Sn今金シー合金重ね合わせて
、トータル17み1a+mになるまで冷間圧延を行ない
、同時に両者を圧着させた。なお、用いたPb−Ca−
5n合金板の組成はCaが0.8%、Snが0.5%で
ある。以上のようにして作製したPb  Sn (0,
05%)合金被覆シートをエキスバンド加工することに
よって55 D 23型電池用の陽極格子体を作製した
A PB-Sn alloy was prepared by adding 0.05% of PB to PB with a purity of 99.99% or higher, and this was added to a thickness of 0.1ta+a.
Rolled to . Next, Pb −Ca − with a thickness of 5Il1m
The Sn alloy plate and the above-mentioned ph-Sn alloy were laminated and cold rolled to a total thickness of 17mm (1a+m), and the two were pressed together at the same time. In addition, the Pb-Ca-
The composition of the 5n alloy plate is 0.8% Ca and 0.5% Sn. Pb Sn (0,
An anode grid for a 55D 23 type battery was prepared by expanding a 05%) alloy coated sheet.

この陽極格子体を用いて55D23型単電池(2v)を
作製成し、(本発明品)過放電放置後の充電回復性 ・
を調べたところ第2図に示すように、Pb−5n(2%
)合金を同様な方法で被覆した場合とほとんど同等の充
電回復性が得られることを確認した。
A 55D23 type unit cell (2V) was made using this anode lattice, and the charge recovery after overdischarging (product of the present invention) was confirmed.
As shown in Figure 2, Pb-5n (2%
) It was confirmed that nearly the same charge recovery properties as those obtained when the alloy was coated using a similar method were obtained.

なお、陰極格子体にはPbCa−5n合金から成る二キ
愚バンド加工格子を用い、その組成はCa:0.8%、
Sn:0,5%である。また、過放電放置条件および充
電条件は以下のごとくである。
The cathode lattice used was a Nikiwa band-processed lattice made of PbCa-5n alloy, and its composition was Ca: 0.8%;
Sn: 0.5%. In addition, over-discharge leaving conditions and charging conditions are as follows.

過放電放置条件 ・過放電・・・25°C1定抵抗(0,86Ω)放電7
日間・放 置・・・40°C156日間 充電条件・・・・・25°C5定電圧(2,5V)充電
、最大5A 発明の効果 本発明によってCa電池の最大の欠点である過放電放置
後の充電回復性能をSoの添加量を微小としながらも向
上させることがでさた。Pb−5r+今金中のSnの添
加量は0.01〜0.2%と非常に少量であるため高価
なSnを使用することによるコストアップの問題がほと
んどない。
Overdischarge condition/overdischarge...25°C1 constant resistance (0.86Ω) discharge 7
Days/Leaving: 40°C 156 days Charging conditions: 25°C 5 constant voltage (2.5V) charging, maximum 5A Effects of the Invention The present invention eliminates the biggest drawback of Ca batteries after over-discharging and leaving. It was possible to improve the charge recovery performance of the battery while adding only a small amount of So. Since the amount of Sn added in Pb-5r+now gold is very small at 0.01 to 0.2%, there is almost no problem of cost increase due to the use of expensive Sn.

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

第1図はPb  Sn合金中のSnの添加量と活物質と
の界面に生成するPbOxなる抵抗体の厚みとの関係を
示す曲線図、第2図は本発明による格子体を用いた電池
の過放電放置後の充電回復性を示す曲線図である。
Figure 1 is a curve diagram showing the relationship between the amount of Sn added in the PbSn alloy and the thickness of the PbOx resistor formed at the interface with the active material, and Figure 2 is a curve diagram showing the relationship between the amount of Sn added in the PbSn alloy and the thickness of the PbOx resistor formed at the interface with the active material. FIG. 3 is a curve diagram showing charge recovery properties after being left over-discharged.

Claims (1)

【特許請求の範囲】[Claims] 鉛−カルシウム−錫合金より成る格子体表面の一部が、
純度99.99%以上の鉛に錫を0.01〜0.2%添
加した鉛−錫合金で被覆されたことを特徴とする鉛蓄電
池用格子体。
A part of the lattice surface made of lead-calcium-tin alloy is
A grid for a lead-acid battery characterized by being coated with a lead-tin alloy made by adding 0.01 to 0.2% tin to lead with a purity of 99.99% or more.
JP62299140A 1987-11-27 1987-11-27 Lead acid battery grid Expired - Lifetime JPH07118320B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP62299140A JPH07118320B2 (en) 1987-11-27 1987-11-27 Lead acid battery grid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP62299140A JPH07118320B2 (en) 1987-11-27 1987-11-27 Lead acid battery grid

Publications (2)

Publication Number Publication Date
JPH01143148A true JPH01143148A (en) 1989-06-05
JPH07118320B2 JPH07118320B2 (en) 1995-12-18

Family

ID=17868638

Family Applications (1)

Application Number Title Priority Date Filing Date
JP62299140A Expired - Lifetime JPH07118320B2 (en) 1987-11-27 1987-11-27 Lead acid battery grid

Country Status (1)

Country Link
JP (1) JPH07118320B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7152749B2 (en) 2001-09-24 2006-12-26 Tech-Source, Inc. All-terrain vehicle shipping package

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7152749B2 (en) 2001-09-24 2006-12-26 Tech-Source, Inc. All-terrain vehicle shipping package
US7438195B2 (en) 2001-09-24 2008-10-21 Tech-Source, Inc. All-terrain vehicle shipping package

Also Published As

Publication number Publication date
JPH07118320B2 (en) 1995-12-18

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