JPS63128552A - Manufacture of paste-type electrode plate for lead storage battery - Google Patents

Manufacture of paste-type electrode plate for lead storage battery

Info

Publication number
JPS63128552A
JPS63128552A JP61274481A JP27448186A JPS63128552A JP S63128552 A JPS63128552 A JP S63128552A JP 61274481 A JP61274481 A JP 61274481A JP 27448186 A JP27448186 A JP 27448186A JP S63128552 A JPS63128552 A JP S63128552A
Authority
JP
Japan
Prior art keywords
paste
grid
belt
electrode plate
lead
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
JP61274481A
Other languages
Japanese (ja)
Inventor
Naoto Hoshihara
直人 星原
Seiji Anzai
安斉　誠二
Masayoshi Yuki
正義 結城
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 JP61274481A priority Critical patent/JPS63128552A/en
Publication of JPS63128552A publication Critical patent/JPS63128552A/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
    • H01M4/64—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • 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)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

PURPOSE:To make it possible to obtain an electrode plate of an excellent rapid discharge property and a long service life, by filling a paste for a grid while delaying the transfer speed of the grid from the speed of a belt. CONSTITUTION:While a belt 1 is rotated at a transfer speed 16m/min, a belt- formed expand grid 2 which consists of an Sn alloy including 0.009 wt% of lead and 0.3 wt% of Sn is loaded over the belt and a pasting machine 3 is moved to spread and fill the paste to the grid 2 to produce a continued electrode plate 4. After that, the electrode plate 4 is cut off into a specific size, and a drying and ageing process is given to make up electrode plates. The transfer speed of the grid 2 is made at 13m/min by controlling the rotation speed of a feed roller, and the electrode plates applied and filled with the paste are used to assemble a cell. Therefore, the service life of the electrode plate can be improved without reducing the initial performance of a maintenance-free type lead storage battery, and the service life of the cell can be extended.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は鉛蓄電池用ペースト式極板の製造法に関するも
のであり、とくに鉛−カルシウム系合金のエキスパンド
格子を用いた電池の寿命の向上をはかるものである。[Detailed Description of the Invention] Industrial Application Field The present invention relates to a method for manufacturing a paste-type electrode plate for a lead-acid battery, and in particular to a method for improving the life of a battery using an expanded lattice of a lead-calcium alloy. It is.

従来の技術 鉛蓄電池用ペースト式極板は、集電体兼活物質の支持体
の働きをもつ鉛合金格子に活物質となるペーストを塗着
してつくられる。これまで格子には鉛−アンチモン合金
からなる鋳造格子が使われてきた。しかしながら、アン
チモンは自己放電を促進するなどの欠点があった。そこ
で新しい格子として、アンチモンを含まない鉛−カルシ
ウム系合金が開発された。ところがこの鉛−カルシウム
系合金は鋳造性が悪いので、合金シートに切れ目を入れ
て展開する、いわゆるエキスパンド方式が開発された。Conventional paste-type electrode plates for lead-acid batteries are made by applying a paste serving as an active material to a lead alloy lattice, which functions as a current collector and a support for the active material. Until now, cast grids made of lead-antimony alloy have been used for grids. However, antimony has drawbacks such as promoting self-discharge. Therefore, a lead-calcium alloy that does not contain antimony was developed as a new lattice. However, this lead-calcium alloy has poor castability, so a so-called expand method was developed in which the alloy sheet is expanded by making cuts in it.

このエキスパンド格子は連続したシートからつくられる
連続格子であり、生産性にすぐれている。This expanded lattice is a continuous lattice made from continuous sheets and has excellent productivity.

この格子にペーストを充填する方法としては、回転ベル
トを用いる充填方式が一般的である。すなわち、ペース
トを充填する台として回転式のベルトを用い、このベル
トの上に格子を載せて、ぺ−スト機を通過させてペース
トを充填し、極板をつくるものである。このペーストを
充填する工程は、ペースト機でペーストを格子目に押し
込み、同時に格子をベルトを押し付けるものであって、
ペーストを充填された格子はベルトと一緒に移動してゆ
く。A common method for filling this grid with paste is a filling method using a rotating belt. That is, a rotary belt is used as a table for filling paste, a grid is placed on top of this belt, and the paste is passed through a paste machine to be filled with paste to produce an electrode plate. The process of filling this paste is to use a paste machine to push the paste into the grid, and at the same time press the grid against the belt.
The grid filled with paste moves together with the belt.

発明が解決しようとした問題点 ところで、このようにしてつくられるエキスパンド極板
を用いた電池は、メンテナンス・フリー形の蓄電池とし
て広く使われており、要求される性能も高率放電の高容
量化、軽量小形化、高負荷長寿命化など多種多様である
。Problems that the invention sought to solve By the way, batteries using expanded electrode plates made in this way are widely used as maintenance-free storage batteries, and the required performance is high capacity with high rate discharge. There are a wide variety of products, including lighter weight, smaller size, higher load and longer life.

本発明はこれらの要求の中から、急放電性能にすぐれし
かも寿命性能の向上をはかる極板の製造法を提供するも
のである。In view of these requirements, the present invention provides a method for manufacturing an electrode plate that has excellent rapid discharge performance and improves life performance.

問題点を解決するための手段 本発明は、回転ベルトの上に格子を配置し、この格子を
ベルトと同じ方向にフィードローラで移動させながらペ
ーストを塗着充填する工程において、ベルトの移動速度
よりも格子の移動速度を遅らせてペーストを格子に充填
することを特徴としたものである。これにより高率放電
にすぐれた電池で、長寿命化をはかるものである。Means for Solving the Problems The present invention provides a process in which a grid is placed on a rotating belt, and the grid is moved in the same direction as the belt by a feed roller to apply and fill the paste. This is also characterized by filling the paste into the grid by slowing down the moving speed of the grid. This results in a battery with excellent high-rate discharge and a long lifespan.

ここでの格子には、鉛−カルシウム合金を用いたエキス
パンド格子を用い、さらに、格子下部よりも下側にペー
ストを押し出すように格子に充填すると一層効果がある
。It is even more effective to use an expanded lattice made of a lead-calcium alloy for the lattice, and to fill the lattice so as to push out the paste below the lower part of the lattice.

また、一般にエキスパンド格子の製造工程において、極
板の両９面にペースト紙をはって、活物質の脱落を防ぐ
方法が用いられているが、本発明はこのペースト紙の有
無による効果の差は見られず、ペースト紙の使用にとら
れれるものではない。Additionally, in the manufacturing process of expanded grids, a method is generally used in which paste paper is applied to both nine sides of the electrode plate to prevent the active material from falling off. is not seen and is not taken into account for the use of paste paper.

作　　用 電池の高率放電性能を良くする手段として、低密度ペー
スト、すなわち高多孔度の活物質を用いて、活物質の利
用率を高める方法がある。これは、極板の多孔度を高く
して中に含浸される硫酸の量を増やすことにより、極板
内部の活物質を反応に寄与させて、活物質の利用率を高
めるものである。As a means of improving the high rate discharge performance of a working cell, there is a method of increasing the utilization rate of the active material by using a low density paste, that is, a highly porous active material. This is to increase the porosity of the electrode plate and increase the amount of sulfuric acid impregnated therein, thereby allowing the active material inside the electrode plate to contribute to the reaction and increasing the utilization rate of the active material.

つまり、高率放電では電解液の硫酸の拡散律則になる傾
向が強く、極板表面が反応して液が内部へ拡散できずに
放電が終了することになる。そのため、極板の多孔度を
高めて、硫酸の含浸量を増やすと、それだけ容量が増え
ることになる。In other words, in high-rate discharge, there is a strong tendency for the diffusion law of sulfuric acid in the electrolytic solution to be applied, and the surface of the electrode plate reacts, and the discharge ends without the solution being able to diffuse into the interior. Therefore, if the porosity of the electrode plate is increased and the amount of sulfuric acid impregnated is increased, the capacity will increase accordingly.

ところで、鉛−カルシウム系合金のエキスパンド格子は
、容量劣化を起こしやすい傾向がある。Incidentally, expanded grids made of lead-calcium alloys tend to suffer from capacity deterioration.

これは格子と活物質との密着性に原因があると考えられ
ている。すなわち、格子と活物質との密着性が悪くなる
と、放電のときに、格子と活物質との界面が反応して硫
酸鉛となり、これが不働態層となって活物質の放電をさ
またげるためである。This is thought to be caused by the adhesion between the lattice and the active material. In other words, if the adhesion between the lattice and the active material deteriorates, during discharge, the interface between the lattice and the active material reacts to form lead sulfate, which becomes a passive layer and prevents the active material from discharging. .

したがって、高率放電性能を高めるために低密度のペー
ストをエキスパンド格子に塗着充填すると、格子と活物
質との密着性が低下する傾向になり、寿命性能が低下す
る。Therefore, when a low-density paste is applied and filled into an expanded lattice in order to improve high-rate discharge performance, the adhesiveness between the lattice and the active material tends to decrease, resulting in a decrease in life performance.

そこで、本発明のベルトと格子の移動速度を異ならせた
製造法により極板をつくると、高率放電性能にもすぐれ
、しかも寿命も長い電池を供給できることがわかった。Therefore, it has been found that by manufacturing electrode plates using the manufacturing method of the present invention in which the moving speeds of the belt and the grid are varied, it is possible to provide a battery that has excellent high rate discharge performance and has a long life.

本発明のようにペーストを充填するときに、ベルトの回
転（移動）速度よりも格子および極板の移動速度を遅く
すると、充填されてベルトに押しつけられたペーストは
、ベルトの移動速度で押されて格子とベルトとの間に高
密度で充填され、格子と活物質との密着性を高めるもの
と考えられる。When filling paste as in the present invention, if the moving speed of the grid and the electrode plate is slower than the rotational (moving) speed of the belt, the filled paste that is pressed against the belt will be pushed at the moving speed of the belt. It is thought that the particles are packed between the lattice and the belt at a high density, thereby increasing the adhesion between the lattice and the active material.

一方、格子よシも上のペーストは充填する力がかかりに
くいので、高多孔度の活物質をつくることができる。こ
のように本発明によると、格子下面近傍および格子より
も下の層は多孔度の小さい緻密な活物質で格子に付着し
、密着性を高めて寿命性能の向上をはかることができ、
格子上面よりも上の層は高多孔度の活物質で高率放電性
能を高めることができると推察される。On the other hand, since the paste on the lattice walls is less likely to be subjected to filling force, it is possible to create a highly porous active material. According to the present invention, the layer near the bottom surface of the lattice and below the lattice is made of a dense active material with low porosity that adheres to the lattice, increasing adhesion and improving life performance.
It is presumed that the layer above the lattice top surface is made of a highly porous active material and can improve high rate discharge performance.

一般にペーストの充填速度はできるだけ速くして生産性
の向上をはかるものであり、この点からベルトの移動速
度を速くし、同時に格子の移動速度も速くする方向にあ
る。しかしながら、本発明ではこの点をよく検討した結
果、これまでとは逆に帯状の長い格子の移動速度をベル
トの移動速度よりも遅くすることにより、すぐれた性能
を有する極板をつくることができた。Generally, the filling speed of the paste is made as fast as possible in order to improve productivity, and from this point of view, there is a trend to increase the moving speed of the belt and at the same time to increase the moving speed of the grid. However, in the present invention, as a result of careful consideration of this point, we were able to create an electrode plate with excellent performance by making the moving speed of the long strip-shaped grid slower than the moving speed of the belt. Ta.

実施例 つぎに実施例で本発明の実施例を図により説明する。Example Next, embodiments of the present invention will be explained with reference to the drawings.

ベルト１を１６ｍ／分の移動速度で回転させながら、そ
の上に鉛−０，０９重量％Ｃａ−０，３重量％Ｓｎ合金
からなる帯状の長いエキスパンド格子２を載せて、ペー
スト機３を通過させ、格子２にペーストを塗着充填して
連続した極板４をつくり、その後所定の寸法に切断して
乾燥・熟成工程を行ない極板をつくった。While rotating the belt 1 at a moving speed of 16 m/min, a long strip-shaped expanded grid 2 made of a lead-0.09 wt.% Ca-0.3 wt.% Sn alloy was placed on top of the belt 1 and passed through a paste machine 3. The grid 2 was coated and filled with paste to produce a continuous electrode plate 4, which was then cut into predetermined dimensions and subjected to a drying and aging process to produce an electrode plate.

なお、ペーストを充填するとき、ベルト１と格子２との
間に敷板（図示せず）をおいてすき間をあけ、格子の下
へペーストが押し出されやすくした。格子の移動速度は
フィードローラ（図示せず）の回転周速度を制御して１
３ｍ／分としてペーストを塗着充填した本発明による極
板を用い、電池Ａを組み立てた。また、比較のため格子
の移動速度をベルトと同じ１６ｍ／分にして充填した極
板を用い、電池Ｂを構成した。In addition, when filling the paste, a bottom plate (not shown) was placed between the belt 1 and the grid 2 to create a gap so that the paste could be easily pushed out under the grid. The moving speed of the grating is controlled by controlling the rotational peripheral speed of a feed roller (not shown).
Battery A was assembled using the electrode plate according to the present invention, which was coated and filled with paste at a speed of 3 m/min. For comparison, battery B was constructed using electrode plates filled with the grid moving at a speed of 16 m/min, the same as that of the belt.

このＡ、Ｂの電池を用いて一１５°Ｃの雰囲気中で３０
ＯＡの放電を行ない、６．○Ｖになるまでの持続時間を
測定した結果、Ａ、Ｂともに２分２゜秒で同じ容量が得
られ、高率放電特性は同等であった。Using these batteries A and B, it was
6. Perform OA discharge; As a result of measuring the duration until the voltage reached ○V, the same capacity was obtained for both A and B in 2 minutes and 2° seconds, and the high rate discharge characteristics were the same.

つぎに２ｓＡで８分の放電を行ない、１４．５Ｖで１６
分の充電（最大電流を２５Ａとした）を１サイクルとし
て繰り返し行なった。そして、３５０サイクルごとに３
０ＯＡ放電を行ない、３０秒巨竜圧が７．２ｖ以下にな
ったときを寿命とした。Next, discharge for 8 minutes at 2 sA, and then discharge at 14.5 V for 16
The battery was repeatedly charged for 20 minutes (maximum current was 25 A) as one cycle. And every 350 cycles 3
0OA discharge was performed, and the life was defined as the time when the giant dragon pressure became 7.2 V or less for 30 seconds.

第２図にその結果を示す。図から明らかなように、本発
明による電池Ａは、電池Ｂに比べ寿命が長いことがわか
った。Figure 2 shows the results. As is clear from the figure, it was found that battery A according to the present invention had a longer lifespan than battery B.

これは、格子の移動速度をベルトのそれよりも遅くする
ことにより、ペーストが格子目の下部及びそれよりも下
側に緻密に塗着充填され、格子近傍及び格子の裏側に高
密度の活物質層が形成されて、格子と活物質との密着性
を高めているからと思われる。しかし、ベルトと同じ速
度で格子を移動させてペーストを塗着充填すると、ペー
ストの充填状態は格子の裏と表でともに同じような低密
度の活物質層となっており、ペーストのつまり具゛　　
合が十分でなかった。このために格子と活物質との密着
性も不十分であり、寿命性能が悪い原因になっていると
思われる。By making the moving speed of the lattice slower than that of the belt, the paste is densely applied and filled at the bottom of the lattice and below it, resulting in a high-density active material layer near the lattice and on the back side of the lattice. This is thought to be because the lattice is formed to increase the adhesion between the lattice and the active material. However, when the paste is applied and filled by moving the grid at the same speed as the belt, the filling state of the paste becomes a low-density active material layer that is the same on both the back and front sides of the grid, and the paste becomes clogged.
The timing was not sufficient. For this reason, the adhesion between the lattice and the active material is also insufficient, which is thought to be the cause of poor life performance.

発明の効果 以上述べた様に、本発明はメンテナンス・フリー形鉛蓄
電池の初期性能を低下させずに極板寿命の向上をはかる
ことができ、電池の長寿命化を高める上でその価値は非
常に大きい。Effects of the Invention As stated above, the present invention can improve the life of the electrode plates without reducing the initial performance of maintenance-free lead-acid batteries, and is extremely valuable in extending the life of the battery. big.

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

第１図は本発明によるペースト充填装置の概略説明図、
第２図はペーストを塗着充填した極板を用いて組立てた
電池の寿命試験結果を示す図である。 １・・・・・・ベルト、２・・・・・・エキスパンド格
子、３・・・・・・ペースト機、４・・・・・・極板。 代理人の氏名　弁理士　中　尾　敏　男　ほか１名／−
−−へ°ルト ？−エキスパンＹ格吾 ３−−−へ°−ストポ（ 第１図　　　　　４−立板 第２図 ブイフルぞ（（回ｐFIG. 1 is a schematic explanatory diagram of a paste filling device according to the present invention;
FIG. 2 is a diagram showing the life test results of batteries assembled using electrode plates coated and filled with paste. 1...belt, 2...expanded grid, 3...paste machine, 4...pole plate. Name of agent: Patent attorney Toshio Nakao and 1 other person/-
−−Helt? -Expan Y Kakugo 3---to °-Stopo (Figure 1 4-Standing board Figure 2 Buifuruzo ((time p

Claims (3)

【特許請求の範囲】[Claims] （１）回転ベルトの上に帯状の長い格子を配置し、フィ
ードローラによりこの格子をベルトと同じ方向に移動さ
せながらペーストを塗着充填する工程において、ベルト
の移動速度よりも格子の移動速度を遅らせてペーストを
塗着充填することを特徴とした鉛蓄電池用ペースト式極
板の製造法。(1) In the process of placing a long strip-shaped grid on a rotating belt and applying and filling the paste while moving the grid in the same direction as the belt using a feed roller, the moving speed of the grid is set lower than the moving speed of the belt. A method for manufacturing paste-type electrode plates for lead-acid batteries, characterized by applying and filling paste with a delay. （２）格子が鉛−カルシウム合金からなるエキスパンド
格子である特許請求の範囲第１項記載の鉛蓄電池用ペー
スト式極板の製造法。(2) The method for manufacturing a paste-type electrode plate for a lead-acid battery according to claim 1, wherein the grid is an expanded grid made of a lead-calcium alloy. （３）ペーストを格子底部よりも下に押し出して充填す
ることを特徴とした特許請求の範囲第１項記載の鉛蓄電
池用ペースト式極板の製造法。(3) The method for manufacturing a paste-type electrode plate for a lead-acid battery according to claim 1, characterized in that the paste is extruded and filled below the bottom of the grid.
JP61274481A 1986-11-18 1986-11-18 Manufacture of paste-type electrode plate for lead storage battery Pending JPS63128552A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP61274481A JPS63128552A (en) 1986-11-18 1986-11-18 Manufacture of paste-type electrode plate for lead storage battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP61274481A JPS63128552A (en) 1986-11-18 1986-11-18 Manufacture of paste-type electrode plate for lead storage battery

Publications (1)

Publication Number Publication Date
JPS63128552A true JPS63128552A (en) 1988-06-01

Family

ID=17542292

Family Applications (1)

Application Number Title Priority Date Filing Date
JP61274481A Pending JPS63128552A (en) 1986-11-18 1986-11-18 Manufacture of paste-type electrode plate for lead storage battery

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JP (1) JPS63128552A (en)

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