JP2022175783A - bipolar lead acid battery - Google Patents

bipolar lead acid battery Download PDF

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JP2022175783A
JP2022175783A JP2021082472A JP2021082472A JP2022175783A JP 2022175783 A JP2022175783 A JP 2022175783A JP 2021082472 A JP2021082472 A JP 2021082472A JP 2021082472 A JP2021082472 A JP 2021082472A JP 2022175783 A JP2022175783 A JP 2022175783A
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positive electrode
lead
negative electrode
lead foil
active material
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JP7057465B1 (en
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彩乃 小出
Ayano Koide
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Furukawa Electric Co Ltd
Furukawa Battery Co Ltd
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Furukawa Battery Co Ltd
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    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

To improve adhesion between a lead foil made of a lead alloy having high corrosion resistance and an active material layer in a bipolar lead acid battery having a lead foil made of a lead alloy having high corrosion resistance as a current collecting plate.SOLUTION: A positive electrode lead foil and a negative electrode lead foil have a portion which is a granular structure. At least one of an interface with a positive electrode active material layer 111b of the positive electrode lead foil 111a and an interface with a negative electrode active material layer 112b of the negative electrode lead foil 112a has a portion formed in a granular structure, and has ten-point average roughness (RzJIS) of 50 μm or more according to specification of an "appendix JA of JIS B 0601:2013." Maximum height roughness (Rz) according to the specification is less than half of an average grain diameter of particles constituting the granular structure.SELECTED DRAWING: Figure 1

Description

本発明は、双極型鉛蓄電池に関する。 The present invention relates to bipolar lead-acid batteries.

近年、太陽光や風力等の自然エネルギを利用した発電設備が増えている。このような発電設備においては、発電量を制御することができないことから、蓄電池を利用して電力負荷の平準化を図るようにしている。すなわち、発電量が消費量よりも多いときには差分を蓄電池に充電する一方、発電量が消費量よりも小さいときには差分を蓄電池から放電するようにしている。上述した蓄電池としては、経済性や安全性等の観点から、鉛蓄電池が多用されている。このような従来の鉛蓄電池としては、例えば、下記特許文献１に記載された双極型鉛蓄電池が知られている。 In recent years, the number of power generation facilities using natural energy such as sunlight and wind power is increasing. In such power generation equipment, since the amount of power generation cannot be controlled, a storage battery is used to level the power load. That is, when the amount of power generation is greater than the amount of consumption, the storage battery is charged with the difference, and when the amount of power generation is less than the amount of consumption, the difference is discharged from the storage battery. As the storage battery described above, a lead-acid battery is often used from the viewpoint of economy, safety, and the like. As such a conventional lead-acid battery, for example, a bipolar lead-acid battery described in Patent Document 1 below is known.

この双極型鉛蓄電池は、額縁形で樹脂製のフレームの内側に、樹脂製の基板が取り付けられている。基板の両面には鉛層が配置されている。基板の一面の鉛層には、正極用活物質層が隣接し、他面の鉛層には、負極用活物質層が隣接している。また、額縁形で樹脂製のスペーサを有し、その内側には、電解液を含浸させたガラスマットが配設されている。そして、フレームとスペーサとを交互に複数積層し、フレームとスペーサとの間が接着剤等で接着されている。また、基板に設けた貫通穴を介して、基板の両面の鉛層が接続されている。 This bipolar lead-acid battery is frame-shaped and has a resin substrate attached to the inside of a resin frame. A lead layer is placed on both sides of the board. The positive electrode active material layer is adjacent to the lead layer on one surface of the substrate, and the negative electrode active material layer is adjacent to the lead layer on the other surface. A frame-shaped spacer made of resin is provided, and a glass mat impregnated with an electrolytic solution is disposed inside the spacer. A plurality of frames and spacers are alternately laminated, and the frames and spacers are adhered with an adhesive or the like. Also, the lead layers on both sides of the substrate are connected via through holes provided in the substrate.

すなわち、特許文献１に記載された双極型鉛蓄電池は、鉛または鉛合金からなる正極用鉛箔の一面に正極用活物質層が配置されている正極、鉛または鉛合金からなる負極用鉛箔の一面に負極用活物質層が配置されている負極、および正極と負極との間に介在するセパレータ（ガラスマット）を備え、間隔を開けて積層配置された、複数のセル部材と、複数のセル部材を個別に収容する複数の空間を形成する、複数の空間形成部材と、を有する。 That is, the bipolar lead-acid battery described in Patent Document 1 includes a positive electrode in which a positive electrode active material layer is disposed on one surface of a positive electrode lead foil made of lead or a lead alloy, and a negative electrode lead foil made of lead or a lead alloy. a plurality of cell members which are stacked with a gap therebetween, and which include a negative electrode having a negative electrode active material layer disposed on one surface thereof, and a separator (glass mat) interposed between the positive electrode and the negative electrode; and a plurality of space forming members that form a plurality of spaces for individually accommodating the cell members.

また、空間形成部材は、セル部材の正極側および負極側の少なくとも一方を覆う基板と、セル部材の側面を囲う枠体（二極式プレートおよび端部プレートの枠部とスペーサ）と、を含んでいる。さらに、セル部材と空間形成部材の基板とが交互に積層状態で配置され、隣り合うセル部材の間に配置された基板は、板面と交差する方向に延びる貫通穴を有し、貫通穴の中で、隣り合うセル部材の正極用鉛箔と負極用鉛箔とが導通されて複数のセル部材が直列に電気的に接続され、隣接する枠体が接合されている。 In addition, the space forming member includes a substrate covering at least one of the positive electrode side and the negative electrode side of the cell member, and a frame surrounding the side surface of the cell member (frames and spacers of the bipolar plates and the end plates). I'm in. Further, the cell members and the substrates of the space forming members are alternately arranged in a stacked state, and the substrates arranged between the adjacent cell members have through holes extending in a direction intersecting the plate surface. Among them, the positive electrode lead foil and the negative electrode lead foil of adjacent cell members are electrically connected to electrically connect the plurality of cell members in series, and the adjacent frames are joined.

特許第６１２４８９４号公報Japanese Patent No. 6124894

鉛蓄電池の劣化原因の一つに、正極集電板の腐食がある。電池使用期間が長くなるほど、正極集電板の腐食は進行し、腐食が進むと正極活物質の保持ができなくなり、電池としての性能が低下してしまう。それだけでなく、腐食によって脱落した正極材（正極集電板または正極活物質）が負極に接してしまった場合、短絡の可能性もある。
特に、バイポーラ鉛蓄電池の場合、電流分布が面での反応となるため、電荷移動抵抗を考慮する必要がなく、集電板を薄くすることが可能であるが、正極と負極との距離が近いため、正極集電板の腐食が多いと致命的な欠陥が生じる恐れがあることから、正極集電板の腐食を抑制する必要がある。しかし、耐食性の高い鉛合金は活物質と反応しにくいことから、耐食性の高い鉛合金からなる鉛箔は活物質層との密着性に劣るものとなっている。 One of the causes of deterioration of lead-acid batteries is corrosion of the positive current collector plate. Corrosion of the positive electrode current collecting plate progresses as the battery usage period becomes longer, and as the corrosion progresses, the positive electrode active material cannot be retained, and the performance as a battery deteriorates. In addition, if the positive electrode material (positive current collecting plate or positive electrode active material) falling off due to corrosion comes into contact with the negative electrode, a short circuit may occur.
In particular, in the case of bipolar lead-acid batteries, the current distribution is a surface reaction, so there is no need to consider charge transfer resistance, and it is possible to make the current collector thinner, but the distance between the positive electrode and the negative electrode is short. Therefore, if the positive electrode current collector plate is heavily corroded, fatal defects may occur. Therefore, it is necessary to suppress the corrosion of the positive electrode current collector plate. However, lead alloys with high corrosion resistance do not easily react with the active material, so that lead foils made of lead alloys with high corrosion resistance are inferior in adhesion to the active material layer.

本発明の課題は、耐食性の高い鉛合金からなる鉛箔を集電板として備えた双極型蓄電池において、耐食性の高い鉛合金からなる鉛箔と活物質層との密着性を向上させることである。 An object of the present invention is to improve the adhesion between a lead foil made of a highly corrosion-resistant lead alloy and an active material layer in a bipolar storage battery including a lead foil made of a highly corrosion-resistant lead alloy as a current collector. .

前述した課題を解決するための本発明の第一態様は、以下の構成(1)～(4)を有する双極型蓄電池である。
(1)鉛または鉛合金からなる正極用鉛箔の一面に正極用活物質層が配置されている正極、鉛または鉛合金からなる負極用鉛箔の一面に負極用活物質層が配置されている負極、および前記正極と前記負極との間に介在するセパレータを備え、間隔を開けて積層配置された、複数のセル部材と、前記複数のセル部材を個別に収容する複数の空間を形成する、複数の空間形成部材と、を有する。 A first aspect of the present invention for solving the aforementioned problems is a bipolar storage battery having the following configurations (1) to (4).
(1) A positive electrode in which a positive electrode active material layer is arranged on one surface of a positive electrode lead foil made of lead or a lead alloy, and a negative electrode active material layer is arranged on one surface of a negative electrode lead foil made of lead or a lead alloy. and a separator interposed between the positive electrode and the negative electrode. , and a plurality of space forming members.

(2)前記空間形成部材は、前記セル部材の前記正極側および前記負極側の両方を覆う合成樹脂製の基板と、前記セル部材の側面を囲う枠体と、を含む。前記セル部材と前記空間形成部材の前記基板とが交互に積層された状態で配置されている。隣接する前記枠体が接合されている。 (2) The space forming member includes a synthetic resin substrate that covers both the positive electrode side and the negative electrode side of the cell member, and a frame that surrounds the side surface of the cell member. The cell members and the substrates of the space forming members are alternately stacked. Adjacent frames are joined together.

(3)前記正極用鉛箔および前記負極用鉛箔は粒状組織である部分を有する。前記正極用鉛箔の前記正極用活物質層との界面および前記負極用鉛箔の前記負極用活物質層との界面の少なくともいずれかは、前記粒状組織に形成された部分を有するとともに、「ＪＩＳ Ｂ ０６０１：２０１３の付属書ＪＡ」の規定による十点平均粗さ（ＲzJIS）が５０μｍ以上であり、前記規定による最大高さ粗さ（Ｒz）が、前記粒状組織を構成する粒子の平均粒子径の１／２よりも小さい。 (3) The positive electrode lead foil and the negative electrode lead foil have a portion with a granular structure. At least one of the interface of the positive electrode lead foil with the positive electrode active material layer and the interface of the negative electrode lead foil with the negative electrode active material layer has a portion formed in the granular structure, and " JIS B 0601:2013 Annex JA” has a ten-point average roughness (RzJIS) of 50 μm or more, and the maximum height roughness (Rz) according to the above-mentioned regulation is the average particle size of the particles constituting the granular structure. Less than 1/2 the diameter.

(4)隣り合う前記セル部材の間に配置された前記基板は、板面と交差する方向に延びる貫通穴を有し、前記貫通穴の中で、隣り合う前記セル部材の前記正極用鉛箔と前記負極用鉛箔とが導通されて、前記複数のセル部材が直列に電気的に接続されている。 (4) The substrate disposed between the adjacent cell members has a through hole extending in a direction intersecting the plate surface, and the positive electrode lead foil of the adjacent cell member is located in the through hole. and the negative electrode lead foil are electrically connected to electrically connect the plurality of cell members in series.

本発明の双極型鉛蓄電池は、耐食性の高い鉛合金からなる鉛箔（集電板）と活物質層との密着性に優れたものとなることが期待できる。 The bipolar lead-acid battery of the present invention can be expected to have excellent adhesion between the lead foil (current collector) made of a highly corrosion-resistant lead alloy and the active material layer.

本発明の一実施形態である双極型鉛蓄電池の概略構成を示す断面図である。1 is a cross-sectional view showing a schematic configuration of a bipolar lead-acid battery that is an embodiment of the present invention; FIG. 図１の双極型鉛蓄電池の部分拡大図である。FIG. 2 is a partially enlarged view of the bipolar lead-acid battery of FIG. 1; No.1の鉛箔の断面の金属組織を示す顕微鏡写真である。1 is a micrograph showing the metallographic structure of the cross section of No. 1 lead foil. No.6の鉛箔の断面の金属組織を示す顕微鏡写真である。2 is a micrograph showing the metallographic structure of the cross section of No. 6 lead foil.

以下、本発明の実施形態について説明するが、本発明は以下に示す実施形態に限定されない。以下に示す実施形態では、本発明を実施するために技術的に好ましい限定がなされているが、この限定は本発明の必須要件ではない。 Embodiments of the present invention will be described below, but the present invention is not limited to the embodiments shown below. In the embodiments shown below, technically preferred limitations are made for implementing the present invention, but the limitations are not essential to the present invention.

〔全体構成〕
先ず、この実施形態の双極（バイポーラ）型鉛蓄電池の全体構成について説明する。
図１に示すように、この実施形態の双極型鉛蓄電池１００は、複数のセル部材１１０と、複数枚のバイプレート（空間形成部材）１２０と、第一のエンドプレート（空間形成部材）１３０と、第二のエンドプレート（空間形成部材）１４０を有する。図１ではセル部材１１０が三個積層された双極型鉛蓄電池１００を示しているが、セル部材１１０の数は電池設計により決定される。また、バイプレート１２０の数はセル部材１１０の数に応じて決まる。 〔overall structure〕
First, the overall configuration of the bipolar lead-acid battery of this embodiment will be described.
As shown in FIG. 1, a bipolar lead-acid battery 100 of this embodiment includes a plurality of cell members 110, a plurality of biplates (space forming members) 120, and a first end plate (space forming member) 130. , has a second end plate (space forming member) 140 . Although FIG. 1 shows a bipolar lead-acid battery 100 in which three cell members 110 are stacked, the number of cell members 110 is determined by battery design. Also, the number of biplates 120 is determined according to the number of cell members 110 .

セル部材１１０の積層方向をＺ方向（図１及び図２の上下方向）とし、Ｚ方向に垂直な方向をＸ方向とする。
セル部材１１０は、正極１１１、負極１１２、およびセパレータ（電解質層）１１３を備えている。セパレータ１１３には電解液が含浸されている。正極１１１は、正極用鉛箔（正極用集電板）１１１ａ，１１１ａａと正極用活物質層１１１ｂを有する。負極１１２は負極用鉛箔（負極用集電板）１１２ａ，１１２ａａと負極用活物質層１１２ｂを有する。セパレータ１１３は、正極１１１と負極１１２との間に介在している。セル部材１１０において、正極用鉛箔１１１ａ，１１１ａａ、正極用活物質層１１１ｂ、セパレータ１１３、負極用活物質層１１２ｂ、および負極用鉛箔１１２ａ，１１２ａａは、この順に積層されている。 The stacking direction of the cell members 110 is defined as the Z direction (vertical direction in FIGS. 1 and 2), and the direction perpendicular to the Z direction is defined as the X direction.
The cell member 110 includes a positive electrode 111 , a negative electrode 112 and a separator (electrolyte layer) 113 . The separator 113 is impregnated with an electrolytic solution. The positive electrode 111 has positive electrode lead foils (positive electrode collector plates) 111a and 111aa and a positive electrode active material layer 111b. The negative electrode 112 has negative electrode lead foils (negative electrode collector plates) 112a and 112aa and a negative electrode active material layer 112b. Separator 113 is interposed between positive electrode 111 and negative electrode 112 . In the cell member 110, the positive electrode lead foils 111a and 111aa, the positive electrode active material layer 111b, the separator 113, the negative electrode active material layer 112b, and the negative electrode lead foils 112a and 112aa are laminated in this order.

Ｚ方向の寸法（厚さ）は、正極用鉛箔１１１ａの方が負極用鉛箔１１２ａより大きく（厚く）、正極用活物質層１１１ｂの方が負極用活物質層１１２ｂより大きい（厚い）。
複数のセル部材１１０は、Ｚ方向に間隔を開けて積層配置され、この間隔の部分にバイプレート１２０の基板１２１が配置されている。つまり、複数のセル部材１１０は、バイプレート１２０の基板１２１を間に挟んだ状態で積層されている。 Regarding the dimension (thickness) in the Z direction, the positive electrode lead foil 111a is larger (thicker) than the negative electrode lead foil 112a, and the positive electrode active material layer 111b is larger (thicker) than the negative electrode active material layer 112b.
A plurality of cell members 110 are stacked and arranged at intervals in the Z direction, and substrates 121 of biplates 120 are arranged at the intervals. That is, the plurality of cell members 110 are stacked with the substrate 121 of the biplate 120 interposed therebetween.

複数枚のバイプレート１２０と第一のエンドプレート１３０と第二のエンドプレート１４０は、複数のセル部材１１０を個別に収容する複数の空間（セル）Ｃを形成するための部材である。
図２に示すように、バイプレート１２０は、平面形状が長方形の基板１２１と、基板１２１の四つの端面を覆う枠体１２２と、基板１２１の両面から垂直に突出する柱部１２３とからなり、基板１２１と枠体１２２と柱部１２３は一体に合成樹脂で形成されている。なお、基板１２１の各面から突出する柱部１２３の数は一つであってもよいし、複数であってもよい。 The plurality of biplates 120, the first end plate 130, and the second end plate 140 are members for forming a plurality of spaces (cells) C that individually accommodate the plurality of cell members 110. As shown in FIG.
As shown in FIG. 2, the biplate 120 includes a substrate 121 having a rectangular planar shape, a frame 122 covering four end surfaces of the substrate 121, and columns 123 projecting vertically from both sides of the substrate 121. The substrate 121, the frame 122 and the pillars 123 are integrally formed of synthetic resin. The number of pillars 123 protruding from each surface of substrate 121 may be one, or may be plural.

Ｚ方向において、枠体１２２の寸法は基板１２１の寸法（厚さ）より大きく、柱部１２３の突出端面間の寸法は枠体１２２の寸法と同じである。そして、複数のバイプレート１２０が枠体１２２および柱部１２３同士を接触させて積層することにより、基板１２１と基板１２１との間に空間Ｃが形成され、互いに接触する柱部１２３同士により、空間ＣのＺ方向の寸法が保持される。 In the Z direction, the dimension of the frame 122 is larger than the dimension (thickness) of the substrate 121 , and the dimension between the projecting end faces of the pillars 123 is the same as the dimension of the frame 122 . By stacking a plurality of biplates 120 with the frames 122 and the pillars 123 in contact with each other, a space C is formed between the substrates 121 and 121, and the pillars 123 in contact with each other form a space C. The Z dimension of C is preserved.

正極用鉛箔１１１ａ，１１１ａａ、正極用活物質層１１１ｂ、負極用鉛箔１１２ａ，１１２ａａ、負極用活物質層１１２ｂ、およびセパレータ１１３には、柱部１２３を貫通させる貫通穴１１１ｃ，１１１ｄ，１１２ｃ，１１２ｄ，１１３ａがそれぞれ形成されている。
バイプレート１２０の基板１２１は、板面を貫通する複数の貫通穴１２１ａを有する。基板１２１の一面に第一の凹部１２１ｂが、他面に第二の凹部１２１ｃが形成されている。第一の凹部１２１ｂの深さは第二の凹部１２１ｃより深い。第一の凹部１２１ｂおよび第二の凹部１２１ｃのＸ方向およびＹ方向の寸法は、正極用鉛箔１１１ａおよび負極用鉛箔１１２ａのＸ方向およびＹ方向の寸法に対応させてある。 Lead foil 111a, 111AA, active substance layer for positive electrode, 111B for positive electrode, 112a, 112AA for negative electrode, 112a, negative electrode 112b, and separator 113, penetrating holes that penetrate the columns 123 111c, 111d, 112c, 112c, 112d and 113a are formed respectively.
A substrate 121 of the biplate 120 has a plurality of through holes 121a passing through the plate surface. A first concave portion 121b is formed on one surface of the substrate 121, and a second concave portion 121c is formed on the other surface. The depth of the first recess 121b is deeper than the second recess 121c. The X-direction and Y-direction dimensions of the first recess 121b and the second recess 121c correspond to the X- and Y-direction dimensions of the positive electrode lead foil 111a and the negative electrode lead foil 112a.

バイプレート１２０の基板１２１は、Ｚ方向で、隣り合うセル部材１１０の間に配置されている。バイプレート１２０の基板１２１は、セル部材１１０の正極１１１の側と、その隣のセル部材１１０の負極１１２の側と、の両方を覆う基板である。バイプレート１２０の基板１２１の第一の凹部１２１ｂに、セル部材１１０の正極用鉛箔１１１ａが接着剤層１５０を介して配置されている。つまり、基板１２１の正極１１１の側の面（第一の凹部１２１ｂの底面）に接着剤で正極用鉛箔１１１ａが固定されている。 Substrates 121 of biplates 120 are positioned between adjacent cell members 110 in the Z direction. The substrate 121 of the biplate 120 is a substrate that covers both the positive electrode 111 side of the cell member 110 and the negative electrode 112 side of the adjacent cell member 110 . The positive electrode lead foil 111 a of the cell member 110 is arranged in the first concave portion 121 b of the substrate 121 of the biplate 120 with an adhesive layer 150 interposed therebetween. That is, the positive electrode lead foil 111a is fixed to the surface of the substrate 121 on the positive electrode 111 side (bottom surface of the first concave portion 121b) with an adhesive.

また、バイプレート１２０の基板１２１の第二の凹部１２１ｃに、セル部材１１０の負極用鉛箔１１２ａが接着剤層１５０を介して配置されている。つまり、基板１２１の負極１１２の側の面（第二の凹部１２１ｃの底面）に接着剤で負極用鉛箔１１２ａが固定されている。
バイプレート１２０の基板１２１の貫通穴１２１ａに導通体１６０が配置され、導通体１６０の両端面は、正極用鉛箔１１１ａおよび負極用鉛箔１１２ａと接触し、結合されている。つまり、導通体１６０により正極用鉛箔１１１ａと負極用鉛箔１１２ａとが電気的に接続されている。その結果、複数のセル部材１１０の全てが電気的に直列に接続されている。 Further, the negative electrode lead foil 112a of the cell member 110 is arranged in the second concave portion 121c of the substrate 121 of the biplate 120 with the adhesive layer 150 interposed therebetween. That is, the negative electrode lead foil 112a is fixed to the surface of the substrate 121 on the negative electrode 112 side (bottom surface of the second recess 121c) with an adhesive.
Conductor 160 is disposed in through-hole 121a of substrate 121 of biplate 120, and both end surfaces of conductor 160 are in contact with and bonded to positive electrode lead foil 111a and negative electrode lead foil 112a. That is, the conductor 160 electrically connects the positive electrode lead foil 111a and the negative electrode lead foil 112a. As a result, all of the plurality of cell members 110 are electrically connected in series.

図１に示すように、第一のエンドプレート１３０は、セル部材１１０の正極側を覆う基板１３１と、セル部材１１０の側面を囲う枠体１３２と、基板１３１の一面（最も正極側に配置されるバイプレート１２０の基板１２１と対向する面）から垂直に突出する柱部１３３とからなる。基板１３１の平面形状は長方形であり、基板１３１の四つの端面が枠体１３２で覆われ、基板１３１と枠体１３２と柱部１３３が一体に合成樹脂で形成されている。なお、基板１３１の一面から突出する柱部１３３の数は一つであってもよいし、複数であってもよいが、柱部１３３と接触させるバイプレート１２０の柱部１２３に対応させる。 As shown in FIG. 1, the first end plate 130 includes a substrate 131 that covers the positive electrode side of the cell member 110, a frame 132 that surrounds the side surface of the cell member 110, and one surface of the substrate 131 (located closest to the positive electrode side). and a pillar portion 133 projecting vertically from the surface of the biplate 120 facing the substrate 121 . The planar shape of the substrate 131 is rectangular, and four end surfaces of the substrate 131 are covered with a frame 132. The substrate 131, the frame 132, and the pillars 133 are integrally formed of synthetic resin. The number of columnar portions 133 protruding from one surface of the substrate 131 may be one or plural, and the columnar portions 133 correspond to the columnar portions 123 of the biplate 120 that come into contact with the columnar portions 133 .

Ｚ方向において、枠体１３２の寸法は基板１３１の寸法（厚さ）より大きく、柱部１３３の突出端面間の寸法は枠体１３２の寸法と同じである。そして、最も外側（正極側）に配置されるバイプレート１２０の枠体１２２および柱部１２３に対して、枠体１３２および柱部１３３を接触させて積層することにより、バイプレート１２０の基板１２１と第一のエンドプレート１３０の基板１３１との間に空間Ｃが形成され、互いに接触するバイプレート１２０の柱部１２３と第一のエンドプレート１３０の柱部１３３とにより、空間ＣのＺ方向の寸法が保持される。 In the Z direction, the dimension of the frame 132 is larger than the dimension (thickness) of the substrate 131 , and the dimension between the projecting end faces of the pillars 133 is the same as the dimension of the frame 132 . Then, the frame 132 and the column 133 are brought into contact with the frame 122 and the column 123 of the biplate 120 arranged on the outermost side (on the positive electrode side) to stack the substrate 121 of the biplate 120 . A space C is formed between the substrate 131 of the first end plate 130, and the dimension of the space C in the Z direction is defined by the columnar portion 123 of the biplate 120 and the columnar portion 133 of the first endplate 130 that are in contact with each other. is retained.

最も外側（正極側）に配置されるセル部材１１０の正極用鉛箔１１１ａａ、正極用活物質層１１１ｂ、およびセパレータ１１３には、柱部１３３を貫通させる貫通穴１１１ｃ，１１１ｄ，１１３ａがそれぞれ形成されている。
第一のエンドプレート１３０の基板１３１の一面に凹部１３１ｂが形成されている。凹部１３１ｂのＸ方向の寸法は、正極用鉛箔１１１ａａのＸ方向の寸法に対応させてある。第一のエンドプレート１３０の基板１３１の一面に配置された正極用鉛箔１１１ａａのＺ方向の寸法は、バイプレート１２０の基板１２１の一面に配置された正極用鉛箔１１１ａのＺ方向の寸法よりも大きい。 Through-holes 111c, 111d, and 113a through which the column portion 133 penetrates are formed in the positive electrode lead foil 111aa, the positive electrode active material layer 111b, and the separator 113 of the cell member 110 arranged on the outermost side (on the positive electrode side), respectively. ing.
A concave portion 131 b is formed on one surface of the substrate 131 of the first end plate 130 . The X-direction dimension of the recess 131b corresponds to the X-direction dimension of the positive electrode lead foil 111aa. The Z-direction dimension of the positive electrode lead foil 111aa arranged on one surface of the substrate 131 of the first end plate 130 is larger than the Z-direction dimension of the positive electrode lead foil 111a arranged on one surface of the substrate 121 of the biplate 120. is also big.

第一のエンドプレート１３０の基板１３１の凹部１３１ｂに、セル部材１１０の正極用鉛箔１１１ａａが接着剤層１５０を介して配置されている。つまり、基板１３１の正極１１１の側の面（凹部１３１ｂの底面）に接着剤で正極用鉛箔１１１ａａが固定されている。
また、第一のエンドプレート１３０は、凹部１３１ｂ内の正極用鉛箔１１１ａａと電気的に接続された正極端子を備えている。 The positive electrode lead foil 111aa of the cell member 110 is arranged in the concave portion 131b of the substrate 131 of the first end plate 130 with the adhesive layer 150 interposed therebetween. That is, the positive electrode lead foil 111aa is fixed to the surface of the substrate 131 on the positive electrode 111 side (bottom surface of the recess 131b) with an adhesive.
The first end plate 130 also has a positive terminal electrically connected to the positive lead foil 111aa in the recess 131b.

第二のエンドプレート１４０は、セル部材１１０の負極側を覆う基板１４１と、セル部材１１０の側面を囲う枠体１４２と、基板１４１の一面（最も負極側に配置されるバイプレート１２０の基板１２１と対向する面）から垂直に突出する柱部１４３とからなる。基板１４１の平面形状は長方形であり、基板１４１の四つの端面が枠体１４２で覆われ、基板１４１と枠体１４２と柱部１４３が一体に合成樹脂で形成されている。なお、基板１４１の一面から突出する柱部１４３の数は一つであってもよいし、複数であってもよいが、柱部１４３と接触させるバイプレート１２０の柱部１２３に対応させる。 The second end plate 140 includes a substrate 141 covering the negative electrode side of the cell member 110, a frame 142 surrounding the side surface of the cell member 110, and one surface of the substrate 141 (the substrate 121 of the biplate 120 arranged closest to the negative electrode side). and a pillar portion 143 projecting vertically from the surface facing the . The planar shape of the substrate 141 is rectangular, and four end surfaces of the substrate 141 are covered with a frame 142. The substrate 141, the frame 142, and the pillars 143 are integrally formed of synthetic resin. The number of columnar portions 143 protruding from one surface of the substrate 141 may be one or plural, and the columnar portions 143 are made to correspond to the columnar portions 123 of the biplate 120 that come into contact with each other.

Ｚ方向において、枠体１４２の寸法は基板１３１の寸法（厚さ）より大きく、二つの柱部１４３の突出端面間の寸法は枠体１４２の寸法と同じである。そして、最も外側（負極側）に配置されるバイプレート１２０の枠体１２２および柱部１２３に対して、枠体１４２および柱部１４３を接触させて積層することにより、バイプレート１２０の基板１２１と第二のエンドプレート１４０の基板１４１との間に空間Ｃが形成され、互いに接触するバイプレート１２０の柱部１２３と第二のエンドプレート１４０の柱部１４３とにより、空間ＣのＺ方向の寸法が保持される。 In the Z direction, the dimension of the frame 142 is larger than the dimension (thickness) of the substrate 131 , and the dimension between the projecting end faces of the two pillars 143 is the same as the dimension of the frame 142 . Then, the frame 142 and the column 143 are brought into contact with the frame 122 and the column 123 of the biplate 120 arranged on the outermost side (negative electrode side), thereby laminating the substrate 121 of the biplate 120. A space C is formed between the substrate 141 of the second end plate 140, and the dimension of the space C in the Z direction is defined by the columnar portion 123 of the biplate 120 and the columnar portion 143 of the second endplate 140 that are in contact with each other. is retained.

最も外側（負極側）に配置されるセル部材１１０の負極用鉛箔１１２ａａ、負極用活物質層１１２ｂ、およびセパレータ１１３には、柱部１４３を貫通させる貫通穴１１２ｃ，１１２ｄ，１１３ａがそれぞれ形成されている。
第二のエンドプレート１４０の基板１４１の一面に凹部１４１ｂが形成されている。凹部１４１ｂのＸ方向およびＹ方向の寸法は、負極用鉛箔１１２ａａのＸ方向およびＹ方向の寸法に対応させてある。第二のエンドプレート１４０の基板１４１の一面に配置された負極用鉛箔１１２ａａのＺ方向の寸法は、バイプレート１２０の基板１２１の他面に配置された負極用鉛箔１１２ａのＺ方向の寸法よりも大きい。 Through-holes 112c, 112d, and 113a through which the column portion 143 penetrates are formed in the negative electrode lead foil 112aa, the negative electrode active material layer 112b, and the separator 113 of the cell member 110 arranged on the outermost side (negative electrode side). ing.
A concave portion 141 b is formed on one surface of the substrate 141 of the second end plate 140 . The X-direction and Y-direction dimensions of the recess 141b correspond to the X- and Y-direction dimensions of the negative electrode lead foil 112aa. The Z-direction dimension of the negative electrode lead foil 112aa arranged on one surface of the substrate 141 of the second end plate 140 corresponds to the Z-direction dimension of the negative electrode lead foil 112a arranged on the other surface of the substrate 121 of the biplate 120. bigger than

第二のエンドプレート１４０の基板１４１の凹部１４１ｂに、セル部材１１０の負極用鉛箔１１２ａａが接着剤層１５０を介して配置されている。つまり、基板１４１の負極１１２の側の面（凹部１４１ｂの底面）に接着剤で負極用鉛箔１１２ａａが固定されている。
また、第二のエンドプレート１４０は、凹部１４１ｂ内の負極用鉛箔１１２ａａと電気的に接続された負極端子を備えている。 The negative electrode lead foil 112aa of the cell member 110 is arranged in the concave portion 141b of the substrate 141 of the second end plate 140 with the adhesive layer 150 interposed therebetween. That is, the negative electrode lead foil 112aa is fixed to the surface of the substrate 141 on the negative electrode 112 side (bottom surface of the recess 141b) with an adhesive.
The second end plate 140 has a negative terminal electrically connected to the negative lead foil 112aa in the recess 141b.

なお、上記説明から分かるように、バイプレート１２０は、セル部材１１０の正極側および負極側の両方を覆う基板１２１と、セル部材１１０の側面を囲う枠体１２２と、を含む空間形成部材である。第一のエンドプレート１３０は、セル部材１１０の正極側のみ（正極側および負極側の一方）を覆う基板１３１と、セル部材１１０の側面を囲う枠体１３２と、を含む空間形成部材である。 As can be seen from the above description, the biplate 120 is a space-forming member that includes a substrate 121 that covers both the positive electrode side and the negative electrode side of the cell member 110 and a frame 122 that surrounds the side surfaces of the cell member 110. . The first end plate 130 is a space forming member including a substrate 131 covering only the positive electrode side (one of the positive electrode side and the negative electrode side) of the cell member 110 and a frame 132 surrounding the side surface of the cell member 110 .

また、第二のエンドプレート１４０は、セル部材１１０の負極側のみ（正極側および負極側の一方）を覆う基板１４１と、セル部材１１０の側面を囲う枠体１４２と、を含む空間形成部材である。つまり、基板１２１，１３１，１４１は、セル部材１１０の正極の側および負極の側の少なくとも一方を覆う基板であり、基板１２１はセル部材１１０の正極の側および負極の側の両方を覆う基板である。また、バイプレート１２０の基板１２１は、セル部材１１０同士の間に配置された基板である。 The second end plate 140 is a space forming member including a substrate 141 covering only the negative electrode side (one of the positive electrode side and the negative electrode side) of the cell member 110 and a frame 142 surrounding the side surface of the cell member 110. be. That is, the substrates 121 , 131 , and 141 are substrates covering at least one of the positive electrode side and the negative electrode side of the cell member 110 , and the substrate 121 is a substrate covering both the positive electrode side and the negative electrode side of the cell member 110 . be. Also, the substrate 121 of the biplate 120 is a substrate arranged between the cell members 110 .

〔集電板の構成〕
バイプレート１２０の凹部１２１ｂに配置される正極用鉛箔１１１ａは、例えば、厚さが０．５ｍｍ未満（例えば０．１ｍｍ以上０．４ｍｍ以下）であり、錫（Ｓｎ）の含有率が１．０質量％以上２．０質量％以下であり、カルシウム（Ｃａ）の含有率が０．００５質量％以上０．０３０質量％以下であり、残部が鉛（Ｐｂ）と不可避的不純物である鉛合金からなる圧延シートの熱処理材で形成されている。この熱処理材の組織は粒状組織となっている。 [Structure of current collector]
The positive electrode lead foil 111a disposed in the concave portion 121b of the biplate 120 has, for example, a thickness of less than 0.5 mm (eg, 0.1 mm or more and 0.4 mm or less) and a tin (Sn) content of 1.0 mm. A lead alloy having a content of 0 mass% or more and 2.0 mass% or less, a calcium (Ca) content of 0.005 mass% or more and 0.030 mass% or less, and the balance being lead (Pb) and inevitable impurities. It is formed of a heat-treated material of a rolled sheet consisting of The structure of this heat-treated material is a granular structure.

第一のエンドプレート１３０の凹部１３１ｂに配置される正極用鉛箔１１１ａａは、例えば、厚さが０．５ｍｍ以上１．５ｍｍ以下であり、正極用鉛箔１１１ａと同じ熱処理材で形成されている。
また、正極用鉛箔１１１ａ，１１１ａａの正極用活物質層１１１ｂとの界面は、「ＪＩＳ Ｂ ０６０１：２０１３の付属書ＪＡ」の規定による十点平均粗さ（ＲzJIS）が５０μｍ以上であり、上記規定による最大高さ粗さ（Ｒz）が、正極用鉛箔１１１ａ，１１１ａａの粒状組織を構成する粒子の平均粒子径の１／２よりも小さくなっている。 The positive electrode lead foil 111aa arranged in the concave portion 131b of the first end plate 130 has a thickness of, for example, 0.5 mm or more and 1.5 mm or less, and is made of the same heat treatment material as the positive electrode lead foil 111a. .
In addition, the interface between the positive electrode lead foils 111a and 111aa and the positive electrode active material layer 111b has a ten-point average roughness (RzJIS) of 50 μm or more according to the provisions of “JIS B 0601:2013 Annex JA”, and the above The specified maximum height roughness (Rz) is smaller than 1/2 of the average particle diameter of the particles forming the granular structure of the positive electrode lead foils 111a and 111aa.

バイプレート１２０の凹部１２１ｃに配置される負極用鉛箔（負極用集電板）１１２ａの厚さは、例えば、０．０５ｍｍ以上０．３ｍｍ以下である。負極用鉛箔１１２ａをなす合金は、例えば、錫（Ｓｎ）の含有率が０．５質量％以上２質量％以下の鉛合金である。
第二のエンドプレート１４０の凹部１４１ｂに配置される負極用鉛箔（負極用集電板）１１２ａは、例えば、厚さが０．５ｍｍ以上１．５ｍｍ以下であり、錫（Ｓｎ）の含有率が０．５質量％以上２質量％以下の鉛合金からなる。 The thickness of the negative electrode lead foil (negative electrode collector plate) 112a arranged in the concave portion 121c of the biplate 120 is, for example, 0.05 mm or more and 0.3 mm or less. The alloy forming the negative electrode lead foil 112a is, for example, a lead alloy having a tin (Sn) content of 0.5% by mass or more and 2% by mass or less.
The negative electrode lead foil (negative electrode current collector plate) 112a arranged in the concave portion 141b of the second end plate 140 has a thickness of, for example, 0.5 mm or more and 1.5 mm or less, and the content of tin (Sn) is is a lead alloy containing 0.5% by mass or more and 2% by mass or less.

〔作用、効果〕
実施形態の双極型鉛蓄電池１００では、正極用鉛箔１１１ａ，１１１ａａが上記鉛合金からなる圧延シートの熱処理材であることから、正極用鉛箔１１１ａ，１１１ａａは粒状組織を有する。よって、正極用鉛箔１１１ａ，１１１ａａは、耐食性に優れたものであるとともに、正極用活物質層１１１ｂとの界面が粒状組織の面となっている。また、正極用鉛箔１１１ａ，１１１ａａの正極用活物質層１１１ｂとの界面は、上記規定による十点平均粗さ（ＲzJIS）が５０μｍ以上（構成ａ）であり、上記規定による最大高さ粗さ（Ｒz）が、正極用鉛箔１１１ａ，１１１ａａの粒状組織を構成する粒子の平均粒子径（Ａ）の１／２よりも小さい（構成ｂ）。 [Action, effect]
In the bipolar lead-acid battery 100 of the embodiment, since the positive electrode lead foils 111a and 111aa are heat-treated rolled sheets made of the lead alloy, the positive electrode lead foils 111a and 111aa have a granular structure. Therefore, the positive electrode lead foils 111a and 111aa have excellent corrosion resistance, and the interface with the positive electrode active material layer 111b has a granular structure. In addition, the interface between the positive electrode lead foils 111a and 111aa and the positive electrode active material layer 111b has a ten-point average roughness (RzJIS) defined above of 50 μm or more (structure a), and a maximum height roughness defined above. (Rz) is smaller than 1/2 of the average particle size (A) of the particles forming the granular structure of the positive electrode lead foils 111a and 111aa (configuration b).

このように、正極用鉛箔１１１ａ，１１１ａａは、耐食性の高い鉛合金からなる鉛箔であるが、正極用活物質層１１１ｂとの界面が上記構成ａと構成ｂの両方を満たすことで、正極用活物質層１１１ｂとの密着性が高いものとなっている。これに伴い、正極用鉛箔１１１ａ，１１１ａａから正極用活物質が脱落しにくくなることで、高い電池性能が維持されるとともに短絡が防止されるため、双極型鉛蓄電池１００の寿命向上効果が期待できる。 As described above, the positive electrode lead foils 111a and 111aa are lead foils made of a highly corrosion-resistant lead alloy. It has high adhesion to the active material layer 111b for use. As a result, the positive electrode active material is less likely to come off from the positive electrode lead foils 111a and 111aa, thereby maintaining high battery performance and preventing short circuits. can.

これに対して、正極用鉛箔１１１ａ，１１１ａａの正極用活物質層１１１ｂとの界面の、上記規定による十点平均粗さ（ＲzJIS）が５０μｍ未満であると、正極用活物質層１１１ｂとの密着性が著しく低いものとなる。また、正極用鉛箔１１１ａ，１１１ａａの上記規定による最大高さ粗さ（Ｒz）がＡ／２以上であると、正極用鉛箔１１１ａ，１１１ａａが腐食し易くなるため、貫通が生じやすくなる。 On the other hand, if the ten-point average roughness (RzJIS) defined above at the interface between the positive electrode lead foils 111a and 111aa and the positive electrode active material layer 111b is less than 50 μm, the interface with the positive electrode active material layer 111b Adhesion becomes remarkably low. Further, when the maximum height roughness (Rz) of the positive electrode lead foils 111a and 111aa defined above is A/2 or more, the positive electrode lead foils 111a and 111aa are likely to corrode, and penetration is likely to occur.

なお、上記実施形態の双極型鉛蓄電池１００では、正極用鉛箔１１１ａ，１１１ａａが粒状組織を有する耐食性の高い鉛合金からなり、その正極用活物質層１１１ｂとの界面が上記構成ａと構成ｂの両方を満たすものとされている。しかし、負極用鉛箔１１２ａ，１１２ａａが粒状組織を有する耐食性の高い鉛合金からなり、その負極用活物質層１１２ｂとの界面が上記構成ａと構成ｂの両方を満たすものとされていれば、負極についても同様の作用、効果（活物質が脱落しにくくなることで、高い電池性能が維持されるとともに短絡が防止される）が得られるものとなる。 In the bipolar lead-acid battery 100 of the above embodiment, the positive electrode lead foils 111a and 111aa are made of a highly corrosion-resistant lead alloy having a granular structure, and the interface with the positive electrode active material layer 111b is the structure a and the structure b. It is assumed that both are satisfied. However, if the negative electrode lead foils 112a and 112aa are made of a highly corrosion-resistant lead alloy having a granular structure, and the interface with the negative electrode active material layer 112b satisfies both the above-described configuration a and configuration b, Similar actions and effects can also be obtained for the negative electrode (since the active material is less likely to fall off, high battery performance is maintained and short-circuiting is prevented).

また、鉛箔の金属組織が粒状組織であっても、活物質層との界面の十点平均粗さ（ＲzJIS）が大きすぎる（表面が粗すぎる）と、部分的に鉛箔が薄くなる箇所が生じることで、電池動作時に鉛箔に貫通が生じる危険性が高くなるため、ＲzJISは５０μｍ以上７０μｍ以下であることが好ましい。同様の理由から、最大高さ粗さ（Ｒｚ）は、十点平均粗さ（Ｒｚ）よりも大きくかつ平均粒子径の１／７以上１／２以下が好ましい。 In addition, even if the metal structure of the lead foil is a granular structure, if the ten-point average roughness (RzJIS) of the interface with the active material layer is too large (the surface is too rough), the lead foil is partially thinned. , the risk of the lead foil penetrating during battery operation increases. For the same reason, the maximum height roughness (Rz) is preferably larger than the ten-point average roughness (Rz) and 1/7 or more and 1/2 or less of the average particle diameter.

［鉛箔の準備］
表１に示すNo.1～No.6の鉛箔を準備した。各鉛箔の厚さは全て０．３５ｍｍとした。
＜サンプルNo.1＞
サンプルNo.1の鉛箔は、カルシウム（Ｃａ）の含有率が０．０３０質量％、錫（Ｓｎ）の含有率が２．０質量％、残部が鉛（Ｐｂ）と不可避的不純物である鉛合金の圧延シートを、３１０℃で５分間、大気雰囲気下で熱処理をしたものである。 [Preparation of lead foil]
Lead foils No. 1 to No. 6 shown in Table 1 were prepared. The thickness of each lead foil was set to 0.35 mm.
<Sample No.1>
The lead foil of sample No. 1 has a calcium (Ca) content of 0.030% by mass, a tin (Sn) content of 2.0% by mass, and the balance is lead (Pb), which is an unavoidable impurity. A rolled sheet of the alloy was heat-treated at 310° C. for 5 minutes in an air atmosphere.

サンプルNo.1の鉛箔について、電子顕微鏡で、シート面に垂直で圧延方向と平行な断面を撮影した。その顕微鏡写真を図３に示す。この画像から分かるように、その組織は粒状組織であり、その平均粒子径は１６０μｍであった。
「ＪＩＳ Ｂ ０６０１：２０１３の付属書ＪＡ」の規定に基づいて、サンプルNo.1の鉛箔の表面状態を計測したところ、十点平均粗さ（ＲzJIS）は２０μｍであり、最大高さ粗さ（Ｒz）は３０μｍであった。 For the lead foil of sample No. 1, a cross section perpendicular to the sheet surface and parallel to the rolling direction was photographed with an electron microscope. A micrograph thereof is shown in FIG. As can be seen from this image, the texture was granular and the average particle size was 160 µm.
When the surface condition of the lead foil of sample No. 1 was measured based on the provisions of "JIS B 0601: 2013 Annex JA", the ten-point average roughness (RzJIS) was 20 μm, and the maximum height roughness (Rz) was 30 μm.

＜サンプルNo.2＞
サンプルNo.1と同じ方法で作製した鉛箔の一方の面を、８００番の紙やすりで擦って、十点平均粗さ（ＲzJIS）が３０μｍで、最大高さ粗さ（Ｒz）が４５μｍとなるようにした。これをサンプルNo.2の鉛箔とした。なお、作製した鉛箔は、No.1の鉛箔と同様に、粒状組織を有し、その平均粒子径は１６０μｍであった。 <Sample No.2>
One surface of the lead foil prepared in the same manner as sample No. 1 was rubbed with 800 sandpaper, and the ten-point average roughness (RzJIS) was 30 μm and the maximum height roughness (Rz) was 45 μm. I made it so that This was used as sample No. 2 lead foil. The lead foil thus produced had a granular structure and an average particle size of 160 μm, like the lead foil of No. 1.

＜サンプルNo.3＞
サンプルNo.1と同じ方法で作製した鉛箔の一方の面を、８０番の紙やすりで擦って、十点平均粗さ（ＲzJIS）が５０μｍで、最大高さ粗さ（Ｒz）が６０μｍとなるようにした。これをサンプルNo.3の鉛箔とした。なお、作製した鉛箔は、No.1の鉛箔と同様に、粒状組織を有し、その平均粒子径は１６０μｍであった。 <Sample No.3>
One surface of the lead foil prepared in the same manner as sample No. 1 was rubbed with No. 80 sandpaper, and the ten-point average roughness (RzJIS) was 50 μm and the maximum height roughness (Rz) was 60 μm. I made it so that This was used as sample No. 3 lead foil. The lead foil thus produced had a granular structure and an average particle size of 160 μm, like the lead foil of No. 1.

＜サンプルNo.4＞
サンプルNo.1と同じ方法で作製した鉛箔の一方の面を、８０番の紙やすりで擦って、十点平均粗さ（ＲzJIS）が５０μｍで、最大高さ粗さ（Ｒz）が７０μｍとなるようにした。これをサンプルNo.4の鉛箔とした。なお、作製した鉛箔は、No.1の鉛箔と同様に、粒状組織を有し、その平均粒子径は１６０μｍであった。 <Sample No.4>
One side of the lead foil prepared in the same manner as Sample No. 1 was rubbed with No. 80 sandpaper, and the ten-point average roughness (RzJIS) was 50 μm and the maximum height roughness (Rz) was 70 μm. I made it so that This was used as sample No. 4 lead foil. The lead foil thus produced had a granular structure and an average particle size of 160 μm, like the lead foil of No. 1.

＜サンプルNo.5＞
サンプルNo.1と同じ方法で作製した鉛箔の一方の面を、４０番の紙やすりで擦って、十点平均粗さ（ＲzJIS）が７０μｍで、最大高さ粗さ（Ｒz）が１１０μｍとなるようにした。これをサンプルNo.5の鉛箔とした。なお、作製した鉛箔は、No.1の鉛箔と同様に、粒状組織を有し、その平均粒子径は１６０μｍであった。 <Sample No.5>
One side of the lead foil prepared in the same manner as sample No. 1 was rubbed with No. 40 sandpaper, and the ten-point average roughness (RzJIS) was 70 μm and the maximum height roughness (Rz) was 110 μm. I made it so that This was used as sample No. 5 lead foil. The lead foil thus produced had a granular structure and an average particle size of 160 μm, like the lead foil of No. 1.

＜サンプルNo.6＞
サンプルNo.6の鉛箔は、カルシウム（Ｃａ）の含有率が０．０３０質量％、錫（Ｓｎ）の含有率が２．０質量％、残部が鉛（Ｐｂ）と不可避的不純物である鉛合金の圧延シートであって、熱処理を施していないものであり、その一方の面を、８０番の紙やすりで擦って、十点平均粗さ（ＲzJIS）が５０μｍで、最大高さ粗さ（Ｒz）が７０μｍとなるようにしたものである。 <Sample No.6>
The lead foil of sample No. 6 has a calcium (Ca) content of 0.030% by mass, a tin (Sn) content of 2.0% by mass, and the balance being lead (Pb) and lead as an unavoidable impurity. It is a rolled sheet of an alloy that has not been heat treated, and one surface of it is rubbed with No. 80 sandpaper to obtain a ten-point average roughness (RzJIS) of 50 μm and a maximum height roughness ( Rz) is set to 70 μm.

サンプルNo.6の鉛箔を、紙やすりで擦る前に、電子顕微鏡で、シート面に垂直で圧延方向と平行な断面を撮影した。その顕微鏡写真を図４に示す。この画像から分かるように、その組織は縞状組織である。 Before rubbing the lead foil of sample No. 6 with sandpaper, a cross section perpendicular to the sheet surface and parallel to the rolling direction was photographed with an electron microscope. A micrograph thereof is shown in FIG. As can be seen from this image, the texture is striped texture.

［腐食試験］
No.1～No.6の各鉛箔について、以下の方法で腐食試験を行った。
各鉛箔を幅１５ｍｍ、長さ７０ｍｍの試験片に切断して、比重１．２８の６０℃硫酸に入れ、１３５０ｍＶの定電位(ｖｓ：Ｈｇ／Ｈｇ2ＳＯ4）で２８日間連続の陽極酸化を行った後、生成酸化物を除去した。そして、試験前後に質量を測定し、その値から試験による質量の減少量を算出し、試験片の全表面積当たりの質量減少量を腐食量とした。また、腐食試験後の断面（シート面に垂直で圧延方向と平行な断面）を電子顕微鏡（倍率４００倍）で観察し、鉛箔に貫通が生じているか否かを調べた。 [Corrosion test]
Corrosion tests were conducted on each lead foil No. 1 to No. 6 by the following method.
Each lead foil was cut into a test piece of width 15 mm and length 70 mm, placed in 60° C. sulfuric acid having a specific gravity of 1.28, and anodized continuously for 28 days at a constant potential of 1350 mV (vs: Hg/Hg 2 SO 4 ). After performing, the produced oxide was removed. Then, the mass was measured before and after the test, the amount of decrease in mass due to the test was calculated from the measured value, and the amount of decrease in mass per total surface area of the test piece was taken as the amount of corrosion. In addition, the cross section after the corrosion test (the cross section perpendicular to the sheet surface and parallel to the rolling direction) was observed with an electron microscope (magnification: 400) to examine whether or not the lead foil had penetrated.

［活物質層の剥離試験］
〔バイプレートの作製〕
ＡＢＳ樹脂の射出成形により図１に示す形状のバイプレート１２０を作製した。バイプレート１２０の基板１２１の厚さは２ｍｍである。凹部１２１ｂおよび凹部１２１ｃの底面は、一辺が１０．０ｃｍの正方形であり、凹部１２１ｂおよび凹部１２１ｃの深さは０．３７ｍｍである。 [Peeling Test of Active Material Layer]
[Production of biplate]
A biplate 120 having the shape shown in FIG. 1 was manufactured by injection molding ABS resin. The thickness of the substrate 121 of the biplate 120 is 2 mm. The bottom surfaces of the recesses 121b and 121c are square with sides of 10.0 cm, and the depth of the recesses 121b and 121c is 0.37 mm.

〔エンドプレートの作製〕
ＡＢＳ樹脂の射出成形により図１に示す形状の第一のエンドプレート１３０および第二のエンドプレート１４０を作製した。第一のエンドプレート１３０の基板１３１および第二のエンドプレート１４０の１４１の厚さは１０ｍｍである。凹部１３１ｂおよび凹部１４１ｂの底面は、一辺が１０．０ｃｍｃｍの正方形であり、深さは１．５２ｍｍである。 [Preparation of end plate]
A first end plate 130 and a second end plate 140 having the shape shown in FIG. 1 were produced by injection molding of ABS resin. The thickness of the substrate 131 of the first end plate 130 and 141 of the second end plate 140 is 10 mm. The bottom surfaces of the recess 131b and the recess 141b are square with a side of 10.0 cm cm and a depth of 1.52 mm.

〔双極型鉛蓄電池の組み立て〕
凹部１２１ｂおよび凹部１２１ｃに配置する正極用鉛箔１１１ａおよび負極用鉛箔１１２ａとして、サンプルNo.1～No.6の各鉛箔を一辺が９．０ｃｍの正方形に切り出したものを用いた。これ以外は全て同じにして、図１に示す構造を有し、公称電圧が６ＶであるNo.1～No.6の双極型鉛蓄電池を、通常の方法で組み立てた。つまり、正極用鉛箔および負極用鉛箔の各活物質層側の面の表面状態以外は、各双極型鉛蓄電池で同じ構成とした。 [Assembly of bipolar lead-acid battery]
As the positive electrode lead foil 111a and the negative electrode lead foil 112a arranged in the recess 121b and the recess 121c, squares of 9.0 cm on a side were cut out of the lead foils of samples No. 1 to No. 6, respectively. Otherwise, bipolar lead-acid batteries No. 1 to No. 6 having the structure shown in FIG. 1 and a nominal voltage of 6 V were assembled in the usual manner. In other words, each bipolar lead-acid battery had the same configuration except for the surface state of the positive electrode lead foil and the negative electrode lead foil on the side of each active material layer.

正極用活物質層１１１ｂは、厚さ１．８ｍｍで正極用鉛箔１１１ａ，１１１ａａの表面に形成した。負極用活物質層１１２ｂは、厚さ１．６ｍｍで負極用鉛箔１１２ａ，１１２ａａの表面に形成した。セパレータ１１３は、ガラス繊維からなるものを用いた。電解液としては、通常用いられている濃度の希硫酸を用いた。 The positive electrode active material layer 111b with a thickness of 1.8 mm was formed on the surfaces of the positive electrode lead foils 111a and 111aa. The negative electrode active material layer 112b with a thickness of 1.6 mm was formed on the surfaces of the negative electrode lead foils 112a and 112aa. The separator 113 used was made of glass fiber. Dilute sulfuric acid having a commonly used concentration was used as the electrolytic solution.

〔活物質層の剥離状態の観察〕
組み立てられたNo.1～No.6の双極型鉛蓄電池に対して通常の条件で化成を行った後に、各双極型鉛蓄電池を解体して、正極用鉛箔１１１ａを正極用活物質層１１１ｂから剥がし、正極用鉛箔１１１ａの正極用活物質層１１１ｂ側の面を顕微鏡で観察した。この観察により、正極用鉛箔１１１ａに活物質が残っているかどうかを調べた。活物質の残りが有れば、耐食性の高い鉛合金からなる正極用鉛箔１１１ａに対する正極用活物質層１１１ｂの密着性が優れていると判断できる。 [Observation of Peeling State of Active Material Layer]
After forming the assembled bipolar lead-acid batteries No. 1 to No. 6 under normal conditions, each bipolar lead-acid battery is disassembled, and the positive electrode lead foil 111a is replaced with the positive electrode active material layer 111b. The surface of the positive electrode lead foil 111a on the positive electrode active material layer 111b side was observed with a microscope. Based on this observation, it was determined whether or not the active material remained on the positive electrode lead foil 111a. If the active material remains, it can be determined that the positive electrode active material layer 111b has excellent adhesion to the positive electrode lead foil 111a made of a highly corrosion-resistant lead alloy.

［評価］
腐食試験と剥離試験の結果を、鉛箔の表面状態とともに表１に示す。 [evaluation]
Table 1 shows the results of the corrosion test and the peel test together with the surface condition of the lead foil.

Figure 2022175783000002
Figure 2022175783000002

表１の結果から以下のことが分かる。
No.1～No.5の鉛箔は、粒状組織の鉛合金からなるため耐食性が高い。しかし、No.1とNo.2の鉛箔は、「Ｒz＜Ａ／２」を満たすものの、「ＲzJIS≧５０μｍ」を満たさないため、活物質層の密着性が低いものとなった。また、No.5の鉛箔は、「ＲzJIS≧５０μｍ」を満たすものの、「Ｒz＜Ａ／２」を満たさないため鉛箔に貫通が生じた。これに対して、No.3～No.4の鉛箔は、「Ｒz＜Ａ／２」と「ＲzJIS≧５０μｍ」の両方を満たすため、活物質層の密着性も高く、鉛箔に貫通が生じないものであった。 The results in Table 1 reveal the following.
Lead foils No. 1 to No. 5 are made of a lead alloy with a granular structure and have high corrosion resistance. However, although the lead foils of No. 1 and No. 2 satisfied "Rz<A/2", they did not satisfy "Rz JIS≧50 μm", so that the adhesion of the active material layer was low. Further, the lead foil of No. 5 satisfies "RzJIS≧50 μm", but does not satisfy "Rz<A/2", so that the lead foil penetrates. On the other hand, the lead foils of No. 3 and No. 4 satisfy both "Rz<A/2" and "RzJIS≧50μm", so the adhesion of the active material layer is high, and the lead foil does not penetrate. It did not occur.

さらに、No.6の鉛箔は、縞状組織の鉛合金からなるため耐食性が低いものであった。
よって、No.3～No.4の鉛箔を正極用鉛箔として用いた双極型鉛蓄電池によれば、正極用鉛箔から正極用活物質が脱落しにくくなることで、高い電池性能が維持されるとともに短絡が防止されて、No.1、No.2、No.6の鉛箔を正極用鉛箔として用いた双極型鉛蓄電池よりも寿命が向上すると推定される。 Furthermore, the lead foil of No. 6 was low in corrosion resistance because it was made of a lead alloy with a striped structure.
Therefore, according to the bipolar lead-acid battery using No.3 to No.4 lead foil as the positive electrode lead foil, the positive electrode active material is less likely to fall off from the positive electrode lead foil, thereby maintaining high battery performance. It is presumed that short-circuiting is prevented, and that the life of the bipolar lead-acid battery using No. 1, No. 2, and No. 6 lead foils as positive electrode lead-acid batteries is improved.

１００ 双極（バイポーラ）型鉛蓄電池
１１０ セル部材
１１１ 正極
１１２ 負極
１１１ａ 正極用鉛箔
１１１ａａ 正極用鉛箔（正極用集電板）
１１１ｂ 正極用活物質層
１１２ａ 負極用鉛箔
１１２ａａ 負極用鉛箔（負極用集電板）
１１２ｂ 負極用活物質層
１１３ セパレータ
１２０ バイプレート
１２１ バイプレートの基板（隣り合うセル部材の間に配置された基板）
１２１ａ 基板の貫通穴
１２１ｂ 基板の第一の凹部
１２１ｃ 基板の第二の凹部
１２２ バイプレートの枠体
１３０ 第一のエンドプレート
１３１ 第一のエンドプレートの基板
１３２ 第一のエンドプレートの枠体
１４０ 第二のエンドプレート
１４１ 第二のエンドプレートの基板
１４２ 第二のエンドプレートの枠体
１５０ 接着剤層
１６０ 導通体
Ｃ セル（セル部材を収容する空間） REFERENCE SIGNS LIST 100 bipolar lead-acid battery 110 cell member 111 positive electrode 112 negative electrode 111a positive electrode lead foil 111aa positive electrode lead foil (positive current collector)
111b Active material layer for positive electrode 112a Lead foil for negative electrode 112aa Lead foil for negative electrode (current collector for negative electrode)
112b Negative electrode active material layer 113 Separator 120 Biplate 121 Biplate substrate (substrate disposed between adjacent cell members)
121a Substrate through hole 121b Substrate first recess 121c Substrate second recess 122 Biplate frame 130 First end plate 131 First end plate substrate 132 First end plate frame 140 Second Second end plate 141 Second end plate substrate 142 Second end plate frame 150 Adhesive layer 160 Conductor C Cell (space for accommodating cell members)

Claims (1)

鉛または鉛合金からなる正極用鉛箔の一面に正極用活物質層が配置されている正極、鉛または鉛合金からなる負極用鉛箔の一面に負極用活物質層が配置されている負極、および前記正極と前記負極との間に介在するセパレータを備え、間隔を開けて積層配置された、複数のセル部材と、
前記複数のセル部材を個別に収容する複数の空間を形成する、複数の空間形成部材と、
を有し、
前記空間形成部材は、前記セル部材の前記正極の側および前記負極の側の少なくとも一方を覆う基板と、前記セル部材の側面を囲う枠体と、を含み、
前記セル部材と前記空間形成部材の前記基板とが交互に積層された状態で配置され、隣接する前記枠体が接合され、
前記正極用鉛箔および前記負極用鉛箔は粒状組織である部分を有し、
前記正極用鉛箔の前記正極用活物質層との界面および前記負極用鉛箔の前記負極用活物質層との界面の少なくともいずれかは、前記粒状組織に形成された部分を有するとともに、「ＪＩＳ Ｂ ０６０１：２０１３の付属書ＪＡ」の規定による十点平均粗さ（ＲzJIS）が５０μｍ以上であり、前記規定による最大高さ粗さ（Ｒz）が、前記粒状組織を構成する粒子の平均粒子径の１／２よりも小さく、
隣り合う前記セル部材の間に配置された前記基板は、板面と交差する方向に延びる貫通穴を有し、前記貫通穴の中で、隣り合う前記セル部材の前記正極用鉛箔と前記負極用鉛箔とが導通されて、前記複数のセル部材が直列に電気的に接続されている双極型鉛蓄電池。
A positive electrode in which a positive electrode active material layer is arranged on one surface of a positive electrode lead foil made of lead or a lead alloy, a negative electrode in which a negative electrode active material layer is arranged on one surface of a negative electrode lead foil made of lead or a lead alloy, and a plurality of cell members stacked with a gap therebetween, and a separator interposed between the positive electrode and the negative electrode;
a plurality of space forming members that form a plurality of spaces for individually accommodating the plurality of cell members;
has
The space forming member includes a substrate covering at least one of the positive electrode side and the negative electrode side of the cell member, and a frame surrounding the side surface of the cell member,
the cell members and the substrates of the space forming members are alternately arranged in a laminated state, and the adjacent frames are joined together;
The positive electrode lead foil and the negative electrode lead foil have a portion that is a granular structure,
At least one of the interface of the positive electrode lead foil with the positive electrode active material layer and the interface of the negative electrode lead foil with the negative electrode active material layer has a portion formed in the granular structure, and " JIS B 0601:2013 Annex JA” has a ten-point average roughness (RzJIS) of 50 μm or more, and the maximum height roughness (Rz) according to the above-mentioned regulation is the average particle size of the particles constituting the granular structure. smaller than 1/2 the diameter,
The substrate disposed between the adjacent cell members has a through hole extending in a direction intersecting the plate surface, and the positive electrode lead foil and the negative electrode of the adjacent cell members are located in the through hole. a bipolar lead-acid battery in which the plurality of cell members are electrically connected in series by conducting with the lead foil for the battery.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4726633A (en) * 1971-03-29 1972-10-25
US5800946A (en) * 1996-12-06 1998-09-01 Grosvenor; Victor L. Bipolar lead-acid battery plates
JPH11250894A (en) * 1998-02-26 1999-09-17 Shin Kobe Electric Mach Co Ltd Lead-acid battery, and manufacture thereof
JP2001514794A (en) * 1997-03-12 2001-09-11 ネーデルランセ オルハニサチエ フォール トゥーヘパスト−ナツールウェーテンシャッペルック オンデルズク テーエヌオー Manufacturing method of bipolar plate
JP2004158433A (en) * 2002-10-18 2004-06-03 Furukawa Battery Co Ltd:The Base plate for lead storage battery, and lead storage battery using the same
JP2004186013A (en) * 2002-12-04 2004-07-02 Ntt Power & Building Facilities Inc Electrode collector, its manufacturing method and sealed lead-acid battery
JP2020510968A (en) * 2017-03-03 2020-04-09 イースト ペン マニュファクチャリング カンパニーＥａｓｔ Ｐｅｎｎ Ｍａｎｕｆａｃｔｕｒｉｎｇ Ｃｏ． Bipolar battery and plate

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4726633A (en) * 1971-03-29 1972-10-25
US5800946A (en) * 1996-12-06 1998-09-01 Grosvenor; Victor L. Bipolar lead-acid battery plates
JP2001514794A (en) * 1997-03-12 2001-09-11 ネーデルランセ オルハニサチエ フォール トゥーヘパスト−ナツールウェーテンシャッペルック オンデルズク テーエヌオー Manufacturing method of bipolar plate
JPH11250894A (en) * 1998-02-26 1999-09-17 Shin Kobe Electric Mach Co Ltd Lead-acid battery, and manufacture thereof
JP2004158433A (en) * 2002-10-18 2004-06-03 Furukawa Battery Co Ltd:The Base plate for lead storage battery, and lead storage battery using the same
JP2004186013A (en) * 2002-12-04 2004-07-02 Ntt Power & Building Facilities Inc Electrode collector, its manufacturing method and sealed lead-acid battery
JP2020510968A (en) * 2017-03-03 2020-04-09 イースト ペン マニュファクチャリング カンパニーＥａｓｔ Ｐｅｎｎ Ｍａｎｕｆａｃｔｕｒｉｎｇ Ｃｏ． Bipolar battery and plate

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