JP5787086B2 - Lead-acid battery positive electrode plate and lead-acid battery using the positive electrode plate - Google Patents
Lead-acid battery positive electrode plate and lead-acid battery using the positive electrode plate Download PDFInfo
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Description
本発明は鉛蓄電池の長寿命化に関し、具体的には鉛蓄電池の短寿命化の原因となる正極の格子体腐食による正極板の格子耳部の損壊が抑制できる格子耳部の形状に関する。 The present invention relates to the extension of the life of a lead storage battery, and more specifically to the shape of a lattice ear that can suppress damage to the lattice ear of a positive electrode plate due to corrosion of the positive electrode lattice, which causes a shortened life of the lead storage battery.
据置用や電力貯蔵用などの長寿命が求められる鉛蓄電池は、主に正極格子の腐食による変形、導電性低下で寿命となることが知られている（例えば、特許文献１、２参照）。
その際、格子耳部には応力が集中して、格子耳部が破損する場合や、破損しかかった格子耳部に電流が集中して、格子耳部の溶断を引き起こす場合があるため、格子耳部には一定の強度、すなわち断面積が確保されている。
It is known that lead-acid batteries that are required to have a long life, such as stationary and power storage, have a life mainly due to deformation due to corrosion of the positive grid and a decrease in conductivity (for example, see Patent Documents 1 and 2).
At that time, stress may concentrate on the lattice ears, and the lattice ears may be damaged, or current may concentrate on the damaged lattice ears, causing the lattice ears to melt. The ear portion has a certain strength, that is, a cross-sectional area.
特に、格子体の腐食が主な寿命制限因子の場合、格子部の厚みを厚くすることでも寿命延伸を図ることもできるが、通常は、格子部を厚くするとともに格子耳部も同様に厚くして、その断面積を確保している。しかしながら、格子部や格子耳部の厚みが厚くなると、鋳造巣が形成されやすくなり、特に格子耳部の鋳造巣から腐食が進行して破断に至った場合、短寿命になってしまう問題があった。 In particular, when the corrosion of the grid is the main life limiting factor, it is possible to extend the life by increasing the thickness of the grid, but in general, the thickness of the grid and the grid ears are also increased. The cross-sectional area is secured. However, when the thickness of the lattice part or the lattice edge becomes thick, a casting nest is likely to be formed, and in particular, when corrosion progresses from the casting nest of the lattice edge and breaks, there is a problem that the life becomes short. It was.
このような状況に鑑み、本発明は鉛蓄電池の長寿命化を図るべく、鉛蓄電池の短寿命化の原因となる正極の格子体腐食による正極板の耳部の損壊が抑制できる形状の正極板の格子耳部を提供すると共に、この格子耳部を備える正極板、及び、この正極板を備える制御弁式鉛蓄電池を提供する。 In view of such a situation, the present invention aims at extending the life of the lead-acid battery, and the positive electrode plate having a shape capable of suppressing the damage to the ears of the positive electrode plate due to the corrosion of the positive-electrode lattice that causes the life of the lead-acid battery to be shortened The positive electrode plate provided with this lattice ear | edge part and the control valve type lead acid battery provided with this positive electrode plate are provided.
本発明の第１の発明は、正極活物質が充填された格子部と、その格子部と連続する集電を担う格子耳部から構成される格子体を備えた制御弁式鉛蓄電池用正極板において、前記格子耳部の厚みｔが３ｍｍ以上で、前記格子耳部の幅ｗ［ｍｍ］と厚みｔ［ｍｍ］の比；ｗ／ｔが２．７５以上、３．５０以下、且つ、前記格子体に充填された正極活物質の理論容量Ｃ［Ａｈ］と前記格子耳部の断面積Ｓ［ｍｍ２］との比；Ｃ／Ｓが、２．７５［Ａｈ／ｍｍ２］以上、３．５０［Ａｈ／ｍｍ２］以下であることを特徴とする。 1st invention of this invention is a positive electrode plate for control valve type lead acid batteries provided with the grid | lattice body comprised from the grid | lattice part filled with the positive electrode active material, and the grid | lattice ear | edge part which carries the current collection continuous with the grid | lattice part. The thickness t of the lattice ear is 3 mm or more, and the ratio of the width w [mm] of the lattice ear to the thickness t [mm]; w / t is 2.75 or more, 3.50 or less, and The ratio of the theoretical capacity C [Ah] of the positive electrode active material filled in the lattice body to the cross-sectional area S [mm 2 ] of the lattice ear; C / S is 2.75 [Ah / mm 2 ] or more, 3 .50 [Ah / mm 2 ] or less.
本発明の第２の発明は、第１の発明における正極板を用いたことを特徴とする制御弁式鉛蓄電池（以下、ＶＲＬＡ電池とも称す。）である。 According to a second aspect of the present invention, there is provided a control valve type lead-acid battery (hereinafter also referred to as a VRLA battery) using the positive electrode plate according to the first aspect of the present invention.
本発明によれば、正極板の格子耳部を格子腐食に強い形状とした制御弁式鉛蓄電池の正極板を提供することによって、鉛蓄電池の長寿命化に大きく寄与し、工業上顕著な効果を奏するものである。 According to the present invention, by providing a positive electrode plate of a control valve type lead storage battery in which the grid ear portion of the positive electrode plate has a shape resistant to lattice corrosion, it greatly contributes to the extension of the life of the lead storage battery, and has a remarkable industrial effect. It plays.
図１に、ＶＲＬＡ電池に使用される正極板を構成する格子体の模式図を示す。１は格子体、２は格子部、３は格子耳部である。 FIG. 1 shows a schematic diagram of a lattice body constituting a positive electrode plate used in a VRLA battery. Reference numeral 1 denotes a lattice body, 2 denotes a lattice portion, and 3 denotes a lattice ear portion.
また、格子体１の上端片側に、活物質からの集電をするための格子耳部３が設けられている。
この格子体１の格子耳部３によって形成される格子耳部の代表的な形状を図２に示す。図２において、ｔは格子耳部１２の厚みを表しているが、通常格子耳部１２は、その断面が両凸形状のように作製されるために、一義的に格子耳部の幅を決定できない。
そこで、本発明では、図３に示すように、体積を変化させないで格子耳部１２の断面形状を長方形とした場合の格子耳部の幅を、格子耳部の幅ｗとし、格子耳部の幅ｗと厚みｔを乗じたもの（ｗ×ｔ：ｗｔ）を、その断面積Ｓとして用いている。
In addition, a
A typical shape of the lattice ear formed by the
Therefore, in the present invention, as shown in FIG. 3, when the cross-sectional shape of the
このような正極の格子体腐食について鋭意研究を重ねた結果、格子耳部の形状と格子部に充填する正極活物質量、即ち理論容量で表す値との関係を見出し、本発明に至ったものである。
具体的には、格子耳部の形状のうち、その幅ｗ［ｍｍ］と厚みｔ［ｍｍ］、及び格子耳部の断面積Ｓ［ｍｍ２］が、格子部に充填される正極活物質の理論容量Ｃ［Ａｈ］との関係において、格子腐食に大きく係わることを見出したもので、特に格子耳部の幅ｗと厚みｔの比；ｗ／ｔと、格子部に充填される正極活物質の理論容量Ｃと格子耳部の断面積Ｓとの比；Ｃ／Ｓ［Ａｈ／ｍｍ２］との関係が腐食に対して大きな影響を与えていることを見出した。
As a result of intensive studies on the corrosion of the positive electrode lattice, the present inventors have found the relationship between the shape of the lattice ear and the amount of the positive electrode active material filled in the lattice, that is, the value expressed by the theoretical capacity, and led to the present invention. It is.
Specifically, among the shape of the lattice ear, the width w [mm] and the thickness t [mm], and the cross-sectional area S [mm 2 ] of the lattice ear are the positive electrode active materials filled in the lattice portion. In relation to the theoretical capacity C [Ah], it has been found that it is greatly related to lattice corrosion. In particular, the ratio of the width w to the thickness t of the lattice ear; w / t, and the positive electrode active material filled in the lattice It was found that the relationship between the theoretical capacity C and the cross-sectional area S of the lattice ear; C / S [Ah / mm 2 ] has a great influence on corrosion.
ところで、格子耳部の幅ｗと厚みｔの比；ｗ／ｔは耳部の扁平率を意味している。
一般に、鋳造において、内部に生じる欠陥である鋳造巣は、鋳型に流した溶湯（本願では鉛）が凝固する際の体積変化（収縮）によって形成されることが知られていて、例えば鋳型の形状が円形に近いほど鋳造物は外周部と内部の温度差が大きくなりやすいことから、このような鋳型を用いれば、外周部が冷えて固まる際には内部まで冷えておらず、内部が冷えて固まる際には外周部の鉛は既に凝固して収縮した状態になっているので、内部の鉛を凝固させるだけの体積を確保することができなくなって、その部分が鋳造巣となる。
By the way, the ratio of the width w and the thickness t of the lattice ear; w / t means the flatness of the ear.
In general, in casting, it is known that a casting cavity which is a defect generated inside is formed by a volume change (shrinkage) when a molten metal (lead in this application) solidifies, for example, the shape of the mold. Since the temperature difference between the outer peripheral part and the inner part tends to increase as the shape of the casting becomes closer to a circle, when such a mold is used, when the outer peripheral part cools and hardens, it does not cool down to the inside, and the inside cools down. When solidifying, the lead in the outer peripheral portion has already solidified and contracted, so that it is impossible to secure a volume sufficient to solidify the lead inside, and that portion becomes a casting nest.
そこで、本発明では耳部形状における鋳造巣の発生し難さ、あるいは発生し易さの尺度として、耳部幅と厚みの比；ｗ／ｔ（耳部の扁平率）の範囲を規定した。
その範囲の下限は２．７５で、耳部の厚みが３．０［ｍｍ］以上の場合に、２．７５以上、望ましくは２．７５以上、３．５０以下である。ｗ／ｔが小さいほど正方形に近い断面となり、それが大きいほど扁平な断面となって、極板が当接する面方向の曲げ強度が低下する。特に、正極板では、格子体の腐食が進行すると、極板は縦方向に伸びる傾向があるため、格子耳部やストラップに応力がかかりやすくなることを考慮しつつ物理的強度も考慮して、ｗ／ｔの上限値に対応させてｔの下限値を３ｍｍとしたうえで、経験的に３．５０とした。
なお、格子耳部の厚みが３［ｍｍ］未満の場合には、鋳造巣ができにくいので、ｗ／ｔの値が規定した範囲を逸脱していても、格子耳部に形成される鋳造巣を原因とする格子耳部の損壊は防止できるが、格子耳部の物理的強度を考慮して上記範囲を満足させるようにすることが望ましい。
Therefore, in the present invention, the range of the ratio of the width of the ear portion to the thickness; w / t (the flatness of the ear portion) is defined as a measure of the difficulty of occurrence of the casting nest in the shape of the ear portion or the ease of occurrence.
The lower limit of the range is 2.75, and when the thickness of the ear portion is 3.0 [mm] or more, it is 2.75 or more, preferably 2.75 or more and 3.50 or less. The smaller the w / t, the closer to a square cross-section, and the larger the w / t, the flatter the cross-section, and the bending strength in the surface direction in which the electrode plate abuts decreases. In particular, in the positive electrode plate, as the corrosion of the grid progresses, the electrode plate tends to extend in the vertical direction, so that the physical strength is also taken into account while taking into consideration that stress is easily applied to the lattice ear and the strap, Corresponding to the upper limit value of w / t, the lower limit value of t was set to 3 mm, and empirically set to 3.50.
When the thickness of the lattice ear is less than 3 [mm], it is difficult to form a casting nest. Therefore, even if the w / t value deviates from the specified range, However, it is desirable to satisfy the above range in consideration of the physical strength of the lattice ear.
一方、理論容量と耳部の断面積の比；Ｃ／Ｓが意味するところは、理論容量分の正極活物質量と鋳造巣ができにくい格子耳部の形状を関係付けるものである。
即ち、鋳造巣の発生を防ぐためには、鋳造時における格子耳部の内部の温度勾配を少なくする必要があり、そのための鋳造に係る理論容量と格子耳部の形状、特にその断面積を考慮して、そのＣ／Ｓ［Ａｈ／ｍｍ２］の範囲を、２．７５以上、５．００以下とした。
格子耳部の物理的強度を考慮して、その上限を５．００［Ａｈ／ｍｍ２］とし、鋳造巣が形成されず、物理的強度も確保できることを考慮してその下限を２．７５［Ａｈ／ｍｍ２］とした。
On the other hand, the ratio between the theoretical capacity and the cross-sectional area of the ear portion; C / S means that the amount of the positive electrode active material corresponding to the theoretical capacity is related to the shape of the lattice ear portion that is difficult to form a casting nest.
In other words, in order to prevent the formation of casting voids, it is necessary to reduce the temperature gradient inside the lattice ear during casting. Thus, the range of C / S [Ah / mm 2 ] was set to 2.75 or more and 5.00 or less.
Considering the physical strength of the lattice ear, the upper limit is set to 5.00 [Ah / mm 2 ], and the lower limit is 2.75 [ Ah / mm 2 ].
さらに、鋳造巣が生じない格子耳部を形成するには、先に規定した格子耳部の幅と厚みの比；ｗ／ｔ、及び格子部に充填される正極活物質の理論容量と格子耳部の断面積の比；Ｃ／Ｓの両者の範囲を満足することが重要である。
即ち、格子耳部の幅と厚みの比；ｗ／ｔ（耳部の扁平率）の範囲が、２．７５以上、３．５０以下で、且つ理論容量と格子耳部の断面積との比；Ｃ／Ｓ［Ａｈ／ｍｍ２］の範囲が、２．７５以上、５．００以下である。
Furthermore, in order to form a lattice ear portion where no casting nest is generated, the ratio of the width and thickness of the lattice ear portion defined above; w / t, and the theoretical capacity and lattice ear of the positive electrode active material filled in the lattice portion It is important to satisfy both ranges of the ratio of the cross-sectional area of the part; C / S.
That is, the ratio between the width and thickness of the lattice ear; the range of w / t (ear flatness) is 2.75 or more and 3.50 or less, and the ratio between the theoretical capacity and the cross-sectional area of the lattice ear. The range of C / S [Ah / mm 2 ] is 2.75 or more and 5.00 or less.
以下、実施例を用いて本発明を詳細する。 Hereinafter, the present invention will be described in detail using examples.
格子耳部３の各寸法が異なる、図１のような正極活物質の充填面の厚みが６ｍｍの格子体１をそれぞれ作製した。その耳部寸法を表１に示す。
これらの正極活物質の充填面のデザインは、同一で理論容量２４２ＡｈのＰｂＯ２が充填できるものである。
Each of the lattice bodies 1 having the thickness of the filling surface of the positive electrode active material as shown in FIG. The ear dimensions are shown in Table 1.
The design of the filling surface of these positive electrode active materials is the same, and PbO 2 having a theoretical capacity of 242 Ah can be filled.
表１に示す寸法の格子体をそれぞれ１００枚ずつ、その耳部断面を観察し、耳部断面に鋳造巣が発生している枚数を評価した。その結果を表１に併せて示す。 Each of the 100 lattice bodies having the dimensions shown in Table 1 was observed for the cross section of the ear portion, and the number of cast nests generated in the cross section of the ear portion was evaluated. The results are also shown in Table 1.
さらに、この表１の結果を「耳部幅−耳部厚」関係の散布図に、マッピングした結果を図４に示す。
表１および図４の結果から、ｗ／ｔが２．７５未満では、実施例の範囲内（２．５〜３．５）のＣ／Ｓにおいて、鋳造巣が発生しているが、Ｃ／Ｓの値が大きくなるにつれ、鋳造巣の発生は減少している。一方、Ｃ／Ｓが２．７５未満では、実施例の範囲内（２．５〜３．５）のｗ／ｔにおいて、格子耳部に鋳造巣の発生が見られたが、ｗ／ｔの増加と共に発生頻度は減少している。
Further, the results of Table 1 are mapped to a scatter diagram having a relationship of “ear width-ear thickness”, and the result of mapping is shown in FIG.
From the results shown in Table 1 and FIG. 4, when w / t is less than 2.75, a casting nest is generated in C / S within the range of the example (2.5 to 3.5). As the value of S increases, the occurrence of casting voids decreases. On the other hand, when C / S was less than 2.75, casting nests were observed in the lattice ears at w / t within the range of the example (2.5 to 3.5). The frequency of occurrence decreases with the increase.
従って、格子耳部の幅ｗ［ｍｍ］と、その厚みｔ［ｍｍ］は、その比；ｗ／ｔが２．７５以上で、且つ格子部に充填された正極活物質の理論容量Ｃ［Ａｈ］と格子耳部の断面積Ｓ［ｍｍ２］の比；Ｃ／Ｓが２．７５［Ａｈ／ｍｍ２］以上であれば、鋳造巣が発生しない格子体が得られていることがわかる。 Accordingly, the width w [mm] of the lattice ear portion and the thickness t [mm] thereof are the ratio; w / t is 2.75 or more, and the theoretical capacity C [Ah] of the positive electrode active material filled in the lattice portion. ] And the cross-sectional area S [mm 2 ] of the lattice ear; if C / S is equal to or greater than 2.75 [Ah / mm 2 ], it can be seen that a lattice body in which no casting nest is generated is obtained.
１ 格子体
２ 格子部
３ 格子耳部
１２ 格子耳部
ｗ 格子耳部の幅
ｔ 格子耳部の厚み
Ｃ 格子部に充填される正極活物資の理論容量
Ｓ 格子耳部の断面積
DESCRIPTION OF SYMBOLS 1
Claims (2)
前記格子耳部の厚みｔが３ｍｍ以上で、前記格子耳部の幅ｗ［ｍｍ］と厚みｔ［ｍｍ］の比；ｗ／ｔが２．７５以上、３．５０以下、且つ、
前記格子部に充填された正極活物質の理論容量Ｃ［Ａｈ］と前記格子耳部の断面積Ｓ［ｍｍ２］との比；Ｃ／Ｓが、２．７５［Ａｈ／ｍｍ２］以上、３．５０［Ａｈ／ｍｍ２］以下であることを特徴とする制御弁式鉛蓄電池用正極板。 In a positive electrode plate for a control valve type lead-acid battery comprising a lattice body composed of a lattice portion filled with a positive electrode active material, and a lattice ear portion that carries current collection continuous with the lattice portion,
The thickness t of the lattice ear is 3 mm or more, the ratio of the width w [mm] of the lattice ear to the thickness t [mm]; w / t is 2.75 or more and 3.50 or less, and
Ratio of the theoretical capacity C [Ah] of the positive electrode active material filled in the lattice part to the cross-sectional area S [mm 2 ] of the lattice ear part; C / S is 2.75 [Ah / mm 2 ] or more, 3.50 [Ah / mm < 2 >] or less, The positive electrode plate for control valve type lead acid batteries characterized by the above-mentioned.
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