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JPH0982303A - Separator for sealed lead-acid battery - Google Patents

Separator for sealed lead-acid battery

Info

Publication number
JPH0982303A
JPH0982303A JP7234326A JP23432695A JPH0982303A JP H0982303 A JPH0982303 A JP H0982303A JP 7234326 A JP7234326 A JP 7234326A JP 23432695 A JP23432695 A JP 23432695A JP H0982303 A JPH0982303 A JP H0982303A
Authority
JP
Japan
Prior art keywords
fiber
section
fibers
sheet
glass fibers
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
JP7234326A
Other languages
Japanese (ja)
Other versions
JP3650439B2 (en
Inventor
Masayoshi Tamaki
正芳 田巻
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.)
Hokuetsu Paper Mills Ltd
Original Assignee
Hokuetsu Paper Mills 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 Hokuetsu Paper Mills Ltd filed Critical Hokuetsu Paper Mills Ltd
Priority to JP23432695A priority Critical patent/JP3650439B2/en
Publication of JPH0982303A publication Critical patent/JPH0982303A/en
Application granted granted Critical
Publication of JP3650439B2 publication Critical patent/JP3650439B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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

  • Cell Separators (AREA)

Abstract

PROBLEM TO BE SOLVED: To make the maximum pore diameter small and enhance electrolyte absorbency by combining 50-95wt.% glass fibers having a mean fiber diameter of 2μm or less with 5-50wt.% synthetic fibers having a fiber length of 2-30mm and a modified cross section. SOLUTION: 50-95wt.% glass fibers having a mean fiber diameter of 2μm or less is combined with 5-50wt.% synthetic fibers having a fiber length of 1-30mm and a modified cross section. If the diameters of the glass fibers are excessively large, the maximum pore diameter is made large, the electrolyte holding ability caused by capillary action is decreased, and the stratification preventing effect of an electrolyte becomes insufficient. The synthetic fibers having a modified cross section and also having acid resistance are used and make a sheet bulky. The modified cross section of the fiber increases the stiffness of the fiber, and as a result, the stiffness in the thickness direction of the sheet is increased, and the sheet keeps the thickness when pressed.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【発明の属する技術分野】本発明は蓄電池用セパレー
タ、特にガラス繊維を主体とする密閉型鉛蓄電池用セパ
レータに関するものであり、嵩高でなおかつ最大細孔径
が小さく、高い電解液吸収度を有し、厚さ復元性に優れ
る蓄電池用セパレータを提供することを目的としたもの
である。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a storage battery separator, and more particularly to a sealed lead storage battery separator mainly composed of glass fiber, which is bulky and has a small maximum pore diameter, and has a high electrolyte absorption rate. It is an object of the present invention to provide a storage battery separator that is excellent in thickness restoration.

【0002】[0002]

【従来の技術】従来の蓄電池用セパレータの製造法とし
て、ガラス繊維とアクリル等の合成繊維とからなるスラ
リーを抄紙法によりシート状とし、セパレータを製造す
ることは公知である。しかし合成繊維がガラス繊維に比
べて親水性が低いことから、電解液の吸収性ならびに保
液性が劣るという欠点を有している。
2. Description of the Related Art As a conventional method of manufacturing a separator for a storage battery, it is known to manufacture a separator by making a slurry of glass fibers and synthetic fibers such as acrylic into a sheet by a papermaking method. However, since synthetic fibers are less hydrophilic than glass fibers, they have the drawback of poor electrolyte absorption and liquid retention.

【0003】シートを嵩高にすることで、液体の吸収
性、または緩衝作用として弾力性を与えることが従来よ
り提案されている。これらの技術は、セルローズを主体
としており、これに嵩高性を与えるため、例えば、屈曲
した合成繊維、または三次元捲縮合成繊維(特開平3−
269199号公報)を加えるという手段が取られてい
る。ところがこれらの嵩高シートは、セルローズを主体
としているために、耐薬品性が劣っており、密閉型鉛蓄
電池に使用されるセパレータのように、硫酸等の強酸の
電解液を吸収、保持させる用途には不適当であった。そ
こで、これに改良を加えセルローズのかわりに合成パル
プを主体としたものが提案されている(特開平6−27
2189号公報)。
It has been proposed in the past to make a sheet bulky so as to absorb liquid or provide elasticity as a buffering action. These techniques are mainly based on cellulose, and in order to impart bulkiness to them, for example, a bent synthetic fiber or a three-dimensional crimped synthetic fiber (Japanese Patent Application Laid-Open No. Hei.
No. 269199) is added. However, since these bulky sheets are mainly composed of cellulose, they have poor chemical resistance and are used for absorbing and retaining an electrolytic solution of a strong acid such as sulfuric acid like a separator used in a sealed lead acid battery. Was inappropriate. Therefore, an improvement has been made to this, and one in which synthetic pulp is mainly used instead of cellulose has been proposed (JP-A-6-27).
2189).

【0004】ところが、セルロースまたは合成パルプを
主体としたものは従来のガラス繊維を主体としたものに
比べ嵩高ではあるが最大細孔径が大きいという欠点があ
る。また、最大細孔径を小さくするにはセルロースまた
は合成パルプの濾水度を小さくすることが必要である
が、濾水度が小さくなると繊維間の絡み合いが不十分と
なり、抄紙性が悪化してしまう。一方、従来のガラス繊
維を主体とするものは嵩高性に限界がある。
However, the one mainly composed of cellulose or synthetic pulp is bulky as compared with the one mainly composed of the conventional glass fiber, but has a drawback that the maximum pore diameter is large. Further, in order to reduce the maximum pore size, it is necessary to reduce the freeness of cellulose or synthetic pulp, but when the freeness is low, the entanglement between fibers becomes insufficient and the papermaking property deteriorates. . On the other hand, conventional glass fiber-based products have a limit in bulkiness.

【0005】すなわち、嵩高なシートは最大細孔径が大
きく、最大細孔径が小さいシートは十分な嵩高性が得ら
れない。
That is, a bulky sheet has a large maximum pore diameter, and a sheet having a small maximum pore diameter cannot obtain sufficient bulkiness.

【0006】[0006]

【発明が解決しようとする課題】従って本発明の課題
は、従来のガラス繊維を主体とするシートでは限界のあ
る嵩高性を更に向上しながら、なおかつ最大細孔径が小
さく、高い電解液吸収度を有し、厚さ復元性に優れる、
蓄電池用セパレータを提供することである。
SUMMARY OF THE INVENTION Therefore, the object of the present invention is to further improve the bulkiness, which is limited in the conventional sheet mainly composed of glass fiber, while having a small maximum pore diameter and a high electrolyte absorption. It has, and is excellent in thickness restoration,
It is to provide a separator for a storage battery.

【0007】[0007]

【課題を解決するための手段】この課題は、平均繊維径
2μm 以下のガラス繊維50〜95重量% と繊維長さ2
〜30mmの異型断面を有する合成繊維5〜50重量%
とを組合せてなる密閉型鉛蓄電池用セパレータによって
解決される。
[Means for Solving the Problems] This problem is that 50 to 95% by weight of glass fibers having an average fiber diameter of 2 μm or less and a fiber length of 2
5 to 50% by weight of synthetic fiber having an irregular cross section of -30 mm
This is solved by a sealed lead-acid battery separator formed by combining and.

【0008】[0008]

【発明の実施の形態】本発明で用いられるガラス繊維
は、その繊維径が過度に大きいとセパレータの最大細孔
径が大きくなり、毛細管現象による液保持力が低下して
電解液の成層化防止効果が十分に得られない恐れがある
ので、平均繊維径を2μm 以下、好ましくは1μm 以下
とする。また、逆にガラス繊維の繊維径が小さ過ぎるこ
とはコスト高となってしまうので、0.4μm 以上とす
るのが好適である。すなわち、本発明で使用されるガラ
ス繊維の平均繊維径は、2μm 以下、特に0.4〜1μ
mであるのが望ましい。
BEST MODE FOR CARRYING OUT THE INVENTION In the glass fiber used in the present invention, if the fiber diameter is excessively large, the maximum pore size of the separator becomes large, and the liquid retention force due to the capillary phenomenon is reduced to prevent the electrolyte from being stratified. Therefore, the average fiber diameter is 2 μm or less, preferably 1 μm or less. On the other hand, if the fiber diameter of the glass fiber is too small, the cost will be high. Therefore, 0.4 μm or more is preferable. That is, the average fiber diameter of the glass fibers used in the present invention is 2 μm or less, particularly 0.4 to 1 μm.
Preferably m.

【0009】本発明において、ガラス繊維は平均繊維径
2μm 以下であればよいのであり、2μm 以下の極細ガ
ラス繊維のみでなく、繊維径が2μm を超え30μm 以
下の中細ガラス繊維が含まれていてもよい。このような
中細ガラス繊維を配合することによってガラス繊維の低
コスト化を図ることができるが、中細ガラス繊維の配合
量は多くなると平均細孔径が規定より大きくなるのでガ
ラス繊維の全量を基準として50% 以下とすることが好
ましい。
In the present invention, it suffices that the glass fibers have an average fiber diameter of 2 μm or less, and include not only ultrafine glass fibers having a diameter of 2 μm or less, but also medium-fine glass fibers having a fiber diameter of more than 2 μm and 30 μm or less. Good. Although it is possible to reduce the cost of glass fibers by blending such medium-thin glass fibers, the average pore diameter becomes larger than the regulation when the amount of medium-fine glass fibers is increased, so the total amount of glass fibers is the standard. Is preferably 50% or less.

【0010】本発明において使用する異型断面を有する
合成繊維は、耐酸性であることが好ましい。例えば、ポ
リエチレン、ポリプロピレン等のオレフィンの単独重合
体、エチレンと他のα−オレフィンとの共重合体などの
ポリオレフィン、ポリスチレン、ポリメチルメタクリレ
ート、ポリアクリロニトリル、ポリ塩化ビニル、ポリ塩
化ビニリデン、ナイロン、ポリエステル、ポリフルオロ
エチレンなどの共重合体より得られる各種繊維または複
合繊維等が挙げられる。
The synthetic fibers having atypical cross section used in the present invention are preferably acid resistant. For example, polyethylene, homopolymers of olefins such as polypropylene, polyolefins such as copolymers of ethylene and other α-olefins, polystyrene, polymethylmethacrylate, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, nylon, polyester, Examples include various fibers or composite fibers obtained from a copolymer such as polyfluoroethylene.

【0011】シートに嵩高性を付与するためには、これ
らの各種繊維の断面形態が異型断面を有していることが
重要である。異型断面とは、繊維の断面形態が円形以外
の形状を持つものであり、例えばT型、Y型、X型、□
型、△型、☆型などが挙げられる。すなわり、繊維の断
面形態が前記異型断面を有していることから、湿式抄造
してできあがったシートは繊維間に空間ができるため、
容易に嵩高なシートを得ることができる。さらに、繊維
の断面形態が前記異型断面であることから繊維自身の剛
性が高く、その結果、シートの厚さ方向の剛性が増し、
シートが加圧されたときの厚さの復元性にも優れたもの
となる。なお、これらの合成繊維は、繊維の断面形態が
前記異型断面を持っていることが重要であり、繊維自身
はモノフィラメントであっても、三次元的に捲縮された
ものであってもその効果は変わらないものである。ま
た、これら合成繊維の繊維長は2〜30mmが必要であ
り、繊維長が2mm未満では繊維が短すぎで繊維同士の
絡み合いが少ないため好ましくない。一方、30mmを
超えると分散時の繊維同士の絡み合いが強くなり過ぎて
均一な分散を得ることが困難となる。かかる合成繊維の
配合率は5〜50重量% が必要である。5重量% 未満で
はシート内の嵩高性発現効果が少なく好ましくない。ま
た配合率を多くすると最大細孔径が大きくなることから
50重量% 以下とするのが好ましい。
In order to impart bulkiness to the sheet, it is important that the cross-sectional morphology of these various fibers has an atypical cross section. Atypical cross-sections are those in which the cross-sectional form of the fiber has a shape other than circular, such as T-type, Y-type, X-type, and □.
Type, △ type, ☆ type and so on. That is, since the cross-sectional shape of the fibers has the atypical cross-section, the sheet formed by wet papermaking has a space between the fibers,
A bulky sheet can be easily obtained. Furthermore, since the cross-sectional shape of the fiber is the atypical cross-section, the rigidity of the fiber itself is high, and as a result, the rigidity in the thickness direction of the sheet increases,
The sheet is also excellent in the thickness restoring property when pressed. In addition, it is important for these synthetic fibers that the cross-sectional morphology of the fibers has the atypical cross section, and whether the fibers themselves are monofilaments or three-dimensionally crimped, the effect thereof is obtained. Is the same. Further, the fiber length of these synthetic fibers is required to be 2 to 30 mm, and if the fiber length is less than 2 mm, the fibers are too short and the entanglement between the fibers is small, which is not preferable. On the other hand, if it exceeds 30 mm, the entanglement of fibers during dispersion becomes too strong, and it becomes difficult to obtain uniform dispersion. The blending ratio of such synthetic fiber is required to be 5 to 50% by weight. If it is less than 5% by weight, the effect of developing the bulkiness in the sheet is small, which is not preferable. Further, since the maximum pore diameter increases as the blending ratio increases, it is preferably 50% by weight or less.

【0012】本発明のセパレータは、バインダー等を使
用しなくても良いが、強度付与のために必要に応じて熱
接着性繊維などのバインダーを用いても良い。本発明の
密閉型鉛蓄電池用セパレータは、ガラス繊維と共に異型
断面を有する合成繊維を混抄すること以外は、常法にし
たがって混抄することにより容易に製造できる。
The separator of the present invention does not need to use a binder or the like, but a binder such as a heat-adhesive fiber may be used as necessary for imparting strength. The sealed lead-acid battery separator of the present invention can be easily produced by mixing paper according to a conventional method, except that the synthetic fiber having an atypical cross section is mixed with the glass fiber.

【0013】本発明によれば、異型断面を有する合成繊
維を使用していることから、嵩高で厚さ復元性に優れる
と共に、細径ガラス繊維を主体としていることから、最
大細孔径を小さくすることができる。しかも、得られる
シートは嵩高で最大細孔径が小さいため、電解液の吸
収、保持特性が優れており、しかも厚さ復元性に優れて
いるため、密閉型鉛蓄電池用セパレータに好適に使用さ
れる。
According to the present invention, since synthetic fibers having an atypical cross section are used, they are bulky and have excellent thickness restoration properties, and since they are mainly composed of thin glass fibers, the maximum pore diameter is reduced. be able to. Moreover, since the obtained sheet is bulky and has a small maximum pore size, it has excellent electrolyte absorption and retention properties, and also has excellent thickness restoration properties, and therefore is suitable for use as a sealed lead-acid battery separator. .

【0014】[0014]

【実施例】以下で、実施例および比較例によって本発明
を更に詳細に説明する。実施例1〜3および比較例1〜3 実施例1〜3および比較例1〜3において、表1に示す
抄造原料を配合して、寸法(300×300×1.0)
の密閉型鉛蓄電池用セパレータを製造し、それの諸特性
を測定し、結果を表1に示した。なお、用いた原料の詳
細は次の通りで ある。 極細ガラス繊維: 平均繊維径 0.8μm T型異型断面PET繊維: 繊度3d、繊維長5mm Y型異型断面ナイロン繊維: 繊度3d、繊維長5mm PET繊維: 繊度3d、繊維長5mm PE合成パルプ: 平均繊維径30μm 、平均繊維長1mm なお、実施例、比較例における各特性の測定方法は次の
通りである。 目付: 試料重量を試料面積で除して得られる値であ
る。 厚さ: 試料をその厚み方向に20kg/100cm2
の荷重で押圧した状態で測定する(JIS C−220
2)。 吸液度:試料を垂直にしてその下部を比重1.3の希硫
酸に浸漬し、3分間で液位が上昇する高さを測定するこ
とにより求める。 保液性:重量既知の試料(W1 )を水に浸漬した後、空
中に垂直な状態で30秒間保持した後のセパレータ重量
(W2 )を測定し、保液性=(W2 −W1 )/W1 によ
り求める。 厚さ復元性:試料を5kg/100cm2 の荷重下での
厚さ(T1 )を測定し、同じ場所に20kg/100c
2 の荷重を1分間、負荷する。次に荷重を除き、5k
g/100cm2 の荷重下での厚さ(T2 )を測定す
う。復元性はT2 をT1 で除したものを% で表示したも
のである。 最大細孔径:ASTM−F316−80に従いポロメー
ターにて測定を行う。
EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples. Examples 1 to 3 and Comparative Examples 1 to 3 In Examples 1 to 3 and Comparative Examples 1 to 3, the papermaking raw materials shown in Table 1 were blended to obtain a size (300 × 300 × 1.0).
The sealed lead-acid battery separator of No. 1 was manufactured, various characteristics of the separator were measured, and the results are shown in Table 1. The details of the raw materials used are as follows. Extra fine glass fiber: Average fiber diameter 0.8 μm T-type atypical cross-section PET fiber: Fineness 3d, fiber length 5 mm Y-type atypical cross-section nylon fiber: Fineness 3 d, fiber length 5 mm PET fiber: Fineness 3 d, fiber length 5 mm PE synthetic pulp: Average Fiber diameter 30 μm, average fiber length 1 mm The measuring method of each property in Examples and Comparative Examples is as follows. Unit weight: A value obtained by dividing the sample weight by the sample area. Thickness: 20 kg / 100 cm 2 in the thickness direction of the sample
Measured under the condition of pressing with the load (JIS C-220
2). Liquid absorption: Determined by making the sample vertical and immersing the lower part in dilute sulfuric acid having a specific gravity of 1.3, and measuring the height at which the liquid level rises in 3 minutes. Liquid retention: After dipping a sample (W 1 ) of known weight in water, the weight of the separator (W 2 ) after being held in the air in a vertical state for 30 seconds was measured, and the liquid retention = (W 2 -W 1 ) / W 1 Thickness recovery: The thickness (T 1 ) of a sample under a load of 5 kg / 100 cm 2 was measured, and 20 kg / 100 c was measured at the same place.
Apply a load of m 2 for 1 minute. Next, excluding the load, 5k
The thickness (T 2 ) under a load of g / 100 cm 2 is measured. Restorability is T 2 divided by T 1 expressed in%. Maximum pore diameter: measured with a porometer according to ASTM-F316-80.

【0015】 表1より次のことが明らかである。[0015] The following is clear from Table 1.

【0016】すなわち、本発明によりガラス繊維に異型
断面繊維を混抄することにより、ガラス繊維を主体とし
たセパレータ(比較例1、2)に比べ、嵩高となり、そ
の結果吸液度及び保液性が向上し、厚さ復元性にも優れ
ていることがわかる。また、合成パルプを用いたもの
(比較例3)は、ガラス繊維を主体としたセパレータ
(比較例1、2)に比べ、嵩高で吸液度及び保液性も高
く実施例1〜3と同等にあるが、最大細孔径が大きく、
厚さ復元性も劣っている。
That is, by mixing atypical cross-section fibers with glass fibers according to the present invention, the bulkiness is higher than that of the separators (Comparative Examples 1 and 2) mainly containing glass fibers, and as a result, the liquid absorbency and the liquid retaining property are increased. It can be seen that this is improved and the thickness restoration is also excellent. Further, the one using synthetic pulp (Comparative Example 3) is bulky and has a higher liquid absorption and liquid retention property than those of the separators (Comparative Examples 1 and 2) mainly composed of glass fibers and are equivalent to Examples 1 to 3. However, the maximum pore size is large,
The thickness restoration is also inferior.

【0017】[0017]

【発明の効果】以上に詳述した通り、本発明の密閉型鉛
蓄電池用セパレータによれば、嵩高で最大細孔径が小さ
いため、電解液の吸収、保持特性が良好であり、しかも
厚さ復元性に優れているため、密閉型鉛蓄電池の性能向
上に寄与するところ大である。
As described above in detail, according to the sealed lead-acid battery separator of the present invention, since it is bulky and has a small maximum pore size, it has good absorption and retention characteristics of the electrolytic solution and also has a thickness restoration. Since it has excellent properties, it greatly contributes to the performance improvement of the sealed lead acid battery.

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 平均繊維径2μm 以下のガラス繊維50
〜95重量% と繊維長さ2〜30mmの異型断面を有す
る合成繊維5〜50重量% とを組合せてなる密閉型鉛蓄
電池用セパレータ。
1. A glass fiber 50 having an average fiber diameter of 2 μm or less.
A sealed lead-acid battery separator comprising a combination of ˜95% by weight and 5 to 50% by weight of synthetic fibers having a modified cross section with a fiber length of 2 to 30 mm.
JP23432695A 1995-09-12 1995-09-12 Sealed lead-acid battery separator Expired - Lifetime JP3650439B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP23432695A JP3650439B2 (en) 1995-09-12 1995-09-12 Sealed lead-acid battery separator

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP23432695A JP3650439B2 (en) 1995-09-12 1995-09-12 Sealed lead-acid battery separator

Publications (2)

Publication Number Publication Date
JPH0982303A true JPH0982303A (en) 1997-03-28
JP3650439B2 JP3650439B2 (en) 2005-05-18

Family

ID=16969256

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003308819A (en) * 2002-04-17 2003-10-31 Nippon Muki Co Ltd Separator for sealed lead storage battery, its manufacturing method, and sealed lead storage battery
US7144633B2 (en) 2002-07-29 2006-12-05 Evanite Fiber Corporation Glass compositions
US7160824B2 (en) 2002-07-29 2007-01-09 Evanite Fiber Corporation Glass compositions
WO2019064792A1 (en) * 2017-09-28 2019-04-04 株式会社Gsユアサ Lead storage cell

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003308819A (en) * 2002-04-17 2003-10-31 Nippon Muki Co Ltd Separator for sealed lead storage battery, its manufacturing method, and sealed lead storage battery
US7144633B2 (en) 2002-07-29 2006-12-05 Evanite Fiber Corporation Glass compositions
US7160824B2 (en) 2002-07-29 2007-01-09 Evanite Fiber Corporation Glass compositions
US8012629B2 (en) 2002-07-29 2011-09-06 Hollingsworth & Vose Company Batteries containing bismuth glass compositions
US8211575B2 (en) 2002-07-29 2012-07-03 Hollingsworth & Vose Company Batteries containing bismuth glass compositions
US7939166B2 (en) 2004-07-21 2011-05-10 Hollingsworth & Vose Company Glass compositions
WO2019064792A1 (en) * 2017-09-28 2019-04-04 株式会社Gsユアサ Lead storage cell

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