JP5630716B2 - Lead acid battery - Google Patents

Lead acid battery Download PDF

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JP5630716B2
JP5630716B2 JP2011205826A JP2011205826A JP5630716B2 JP 5630716 B2 JP5630716 B2 JP 5630716B2 JP 2011205826 A JP2011205826 A JP 2011205826A JP 2011205826 A JP2011205826 A JP 2011205826A JP 5630716 B2 JP5630716 B2 JP 5630716B2
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和馬 齋藤
和馬 齋藤
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GS Yuasa International Ltd
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Description

この発明は鉛蓄電池に関する。   The present invention relates to a lead storage battery.

アイドリングストップ車、充電制御車等では、鉛蓄電池は従来よりも充電不足な状態で動作するため、負極に硫酸鉛が蓄積することにより早期に寿命を迎えることがある。負極への硫酸鉛の蓄積はサルフェーションと呼ばれる。この一方で、エンジン始動時の性能等のために、低温HR（高率）放電性能が求められる。さらに電装品が増加し、オールタネータからの電力ではなく鉛蓄電池からの電力を用いる機会が増しているため、鉛蓄電池の高容量化が求められ、この結果、電池の質量が増す傾向にある。   In an idling stop vehicle, a charge control vehicle, and the like, a lead storage battery operates in a state in which charging is insufficient as compared with the conventional case. Therefore, accumulation of lead sulfate in the negative electrode may reach an early life. Accumulation of lead sulfate on the negative electrode is called sulfation. On the other hand, low temperature HR (high rate) discharge performance is required for performance at engine start. Furthermore, since the number of electrical components has increased and the opportunity to use the power from the lead storage battery instead of the power from the alternator has increased, a higher capacity of the lead storage battery is required, and as a result, the mass of the battery tends to increase.

鉛蓄電池の正極板と負極板の格子のマス目は桟により囲まれている。そして格子の桟について、特許文献１（JP2007-123105A）は、桟の縦横比を格子の上部で大きく、下部で小さくすることを提案している。これは、格子の上部では桟を流れる電流が大きく、下部では小さいことに対応している。また特許文献２（WO2007/36979A）は、鉛蓄電池の電解液にアルミニウムイオンとリチウムイオンとを含有させることを提案している。   The grid of the grid of the positive electrode plate and the negative electrode plate of the lead storage battery is surrounded by bars. With respect to grid bars, Patent Document 1 (JP2007-123105A) proposes that the aspect ratio of the bars be large at the top of the grid and small at the bottom. This corresponds to the fact that the current flowing through the crosspiece is large at the top of the grid and small at the bottom. Patent Document 2 (WO2007 / 36979A) proposes that an electrolytic solution of a lead storage battery contains aluminum ions and lithium ions.

JP2007-123105AJP2007-123105A WO2007/36979AWO2007 / 36979A

この発明の課題は、軽量の格子を備え、かつ低温ハイレート放電性能とアイドリングストップ寿命性能とに優れた鉛蓄電池を提供することにある。   An object of the present invention is to provide a lead-acid battery having a light-weight grid and excellent in low-temperature high-rate discharge performance and idling stop life performance.

この発明は、Pb-Ca系合金からなる正極格子を有する正極板と、Pb-Ca系合金からなる格子を有する負極板と、硫酸とアルミニウムイオンとリチウムイオンとを含む電解液とを備えている鉛蓄電池において、
前記正極格子の桟の縦横比が0.6以上0.85以下、または前記負極格子の桟の縦横比が0.5以上0.75以下で、
前記電解液はアルミニウムイオンを0.02mol/L以上0.2mol/L以下、リチウムイオンを0.02mol/L以上0.2mol/L以下含有していることを特徴とする。 The present invention includes a positive electrode plate having a positive electrode lattice made of a Pb-Ca alloy, a negative electrode plate having a lattice made of a Pb-Ca alloy, and an electrolyte containing sulfuric acid, aluminum ions, and lithium ions. In lead-acid batteries,
The aspect ratio of the bars of the positive grid is 0.6 or more and 0.85 or less, or the aspect ratio of the bars of the negative grid is 0.5 or more and 0.75 or less,
The electrolyte aluminum ion 0.02 mol / L or more 0.2 mol / L or less, wherein the lithium ions contains less 0.02 mol / L or more 0.2 mol / L.

好ましくは、前記正極格子の桟の縦横比が0.6以上0.85以下で、かつ前記負極格子の桟の縦横比が0.5以上0.75以下である。
特に好ましくは、前記正極格子の桟の縦横比が0.65以上0.8以下、前記負極格子の桟の縦横比が0.55以上0.7以下である。 Preferably, the aspect ratio of the bars of the positive grid is 0.6 or more and 0.85 or less, and the aspect ratio of the bars of the negative grid is 0.5 or more and 0.75 or less.
Particularly preferably, the aspect ratio of the bars of the positive electrode lattice is 0.65 or more and 0.8 or less, and the aspect ratio of the bars of the negative electrode lattice is 0.55 or more and 0.7 or less.

図４，図５は、アルミニウムイオンとリチウムイオンとを各0.1mol/L含有する電解液を用いた鉛蓄電池に対して、正極格子と負極格子の桟の縦横比を1.0よりも小さくした際の結果を示している。図４，図５から明らかなように、桟の縦横比を小さくすると、アイドリングストップモードでの負極への硫酸鉛の蓄積量(▲)が小さくなり、低温HR放電性能(●)も向上する。図４，図５の試料Blankはアルミニウムイオンもリチウムイオンも含有しない電解液での結果を示し、(▲)と(△)との差は各0.1mol/Lのアルミニウムイオンとリチウムイオンとによる硫酸鉛の蓄積量の低下を、(●)と(○)の差は低温HR放電性能の差を表している。そして桟の縦横比を小さくすると、アルミニウムイオンとリチウムイオンの効果が大きくなることが分かる。また他の条件が同じである場合、格子の質量は桟の縦横比に比例するので、縦横比を小さくすると格子も軽量化し、図４では格子の質量は標準格子の80%で、図５では60%である。   4 and 5 show a case where the aspect ratio of the positive and negative grid bars is smaller than 1.0 with respect to a lead storage battery using an electrolytic solution containing 0.1 mol / L of aluminum ions and lithium ions. Results are shown. As apparent from FIGS. 4 and 5, when the aspect ratio of the crosspiece is reduced, the amount of accumulation of lead sulfate (▲) in the negative electrode in the idling stop mode is reduced, and the low temperature HR discharge performance (●) is also improved. The sample blanks in FIGS. 4 and 5 show the results with an electrolyte solution containing neither aluminum ions nor lithium ions. The difference between (▲) and (△) is the difference between sulfuric acid with 0.1 mol / L aluminum ions and lithium ions. The decrease in lead accumulation, the difference between (●) and (◯) represents the difference in low-temperature HR discharge performance. It can be seen that the effect of aluminum ions and lithium ions increases when the aspect ratio of the crosspiece is reduced. If the other conditions are the same, the mass of the lattice is proportional to the aspect ratio of the crosspiece. Therefore, if the aspect ratio is reduced, the lattice also becomes lighter. In FIG. 4, the mass of the lattice is 80% of the standard lattice. 60%.

図４，図５から、縦横比の効果は正極格子では0.85以下で増し、特に0.8以下で大きくなり、負極格子では0.75以下で増し、特に0.7以下で大きくなることが分かる。一方正極格子で桟の縦横比を0.55以下とすると格子展開時に桟が切れることがあり、負極格子では0.45以下で桟が切れることがあった。また正極格子の桟の縦横比が0.65未満では、格子展開時に格子が曲がることがあった。同様に負極格子の桟の縦横比が0.55未満では、格子が曲がることがあった。しかし、正極格子または負極格子が曲がっても製造上の問題はなかった。これらのことから、桟の縦横比は正極格子では0.6以上、好ましくは0.65以上とし、負極格子では0.5以上、好ましくは0.55以上とする。   4 and 5, it can be seen that the effect of the aspect ratio increases at 0.85 or less in the positive electrode lattice, particularly increases at 0.8 or less, increases at 0.75 or less in the negative electrode lattice, and particularly increases at 0.7 or less. On the other hand, if the cross-sectional aspect ratio of the positive grid is 0.55 or less, the cross may break when the grid is developed, and the cross-cut may break when the negative grid is 0.45 or less. In addition, when the aspect ratio of the positive grid was less than 0.65, the grid could be bent when the grid was developed. Similarly, when the aspect ratio of the negative grid bar is less than 0.55, the grid may be bent. However, there was no problem in manufacturing even if the positive grid or the negative grid was bent. For these reasons, the aspect ratio of the crosspiece is 0.6 or more, preferably 0.65 or more for the positive electrode lattice, and 0.5 or more, preferably 0.55 or more for the negative electrode lattice.

正極格子または負極格子のいずれかが所定の縦横比の桟を備えていれば良いが、好ましくは正極格子の桟の縦横比を0.6以上0.85以下とし、かつ負極格子の桟の縦横比を0.5以上0.75以下とする。特に好ましくは、正極格子の桟の縦横比を0.65以上0.8以下とし、かつ負極格子の桟の縦横比を0.55以上0.7以下とする。   Either the positive grid or the negative grid need only be provided with crosspieces having a predetermined aspect ratio. Preferably, the positive and negative grid bars have an aspect ratio of 0.6 to 0.85, and the negative grid bars have an aspect ratio of 0.5 or more. 0.75 or less. Particularly preferably, the aspect ratio of the bars of the positive electrode grid is 0.65 or more and 0.8 or less, and the aspect ratio of the bars of the negative electrode grid is 0.55 or more and 0.7 or less.

実施例でのアルミニウムイオンとリチウムイオンの濃度の影響を表１に示す。アルミニウムイオンの濃度が0.01mol/Lと0.02mol/Lとでは、アイドリングストップ寿命試験での負極への硫酸鉛の蓄積量に大差があるので、アルミニウムイオンの濃度は0.02mol/L以上とする。またアルミニウムイオンの濃度を0.2mol/Lから0.3mol/Lへ増すと、低温HR放電性能が急激に低下する。従ってアルミニウムイオンの濃度は0.02mol/L以上0.2mol/L以下とする。   Table 1 shows the influence of the concentration of aluminum ions and lithium ions in the examples. When the aluminum ion concentration is 0.01 mol / L and 0.02 mol / L, there is a large difference in the amount of lead sulfate accumulated on the negative electrode in the idling stop life test, so the aluminum ion concentration is 0.02 mol / L or more. In addition, when the aluminum ion concentration is increased from 0.2 mol / L to 0.3 mol / L, the low-temperature HR discharge performance decreases rapidly. Therefore, the concentration of aluminum ions should be 0.02 mol / L or more and 0.2 mol / L or less.

リチウムイオンの濃度を0.01mol/Lから0.02mol/Lへ増すと、低温HR放電性能が急激に向上する。またリチウムイオンの濃度を0.2mol/Lを越えて増しても、さらなる性能の向上は見られない。従ってリチウムイオンの濃度は0.02mol/L以上0.2mol/L以下とする。   When the concentration of lithium ions is increased from 0.01 mol / L to 0.02 mol / L, the low-temperature HR discharge performance is drastically improved. Further, even if the concentration of lithium ions exceeds 0.2 mol / L, no further improvement in performance is observed. Therefore, the lithium ion concentration is set to 0.02 mol / L or more and 0.2 mol / L or less.

実施例での格子の平面図Plan view of the grating in the embodiment 実施例での極板の要部断面図Cross-sectional view of the main part of the electrode plate in the embodiment 実施例の格子のマス目を示す平面図The top view which shows the grid of the grid | lattice of an Example 格子の質量を従来例の80%とした際の、桟の縦横比とアルミニウムイオン及びリチウムイオンの影響を示す特性図Characteristic chart showing the cross-bar aspect ratio and the influence of aluminum ions and lithium ions when the lattice mass is 80% of the conventional example 格子の質量を従来例の60%とした際の、桟の縦横比とアルミニウムイオン及びリチウムイオンの影響を示す特性図Characteristic chart showing the cross-bar aspect ratio and the influence of aluminum ions and lithium ions when the lattice mass is 60% of the conventional example

以下に、本願発明の最適実施例を示す。本願発明の実施に際しては、当業者の常識及び先行技術の開示に従い、実施例を適宜に変更できる。   Hereinafter, an optimum embodiment of the present invention will be described. In carrying out the present invention, the embodiments can be appropriately changed in accordance with common sense of those skilled in the art and disclosure of prior art.

厚さ1.0mmのPb-Ca系合金（Ca：0.07mass%，Sn：1.5mass%，残余はAg，Al等の不純物とPb）を、ロータリーエキスパンド法により正極エキスパンド格子へと加工した。ここで桟の縦横比を0.55〜1.0の範囲で変化させ、格子の質量は標準品（縦横比1.0）の80%，60%の２段階に変化させた。他に桟の縦横比が1.0の標準品（従来例）の格子を作製した。以下桟の縦横比を単に縦横比と呼ぶ。Ca含有量が0.05mass%〜1.0mass%の範囲で、Sn含有量が1.0mass%〜2.0mass%の範囲で、シート厚が0.6mm〜1.2mmの範囲であれば、桟の縦横比、電解液のアルミニウムイオン含有量とリチウムイオン含有量とが同じであることを条件に、正極板の性能は実施例と同等になる。また桟の縦横比を同じにすると、正極格子の質量はほぼシート厚の２乗に比例し、シート厚を増すと格子の質量が増す。   A 1.0 mm thick Pb—Ca-based alloy (Ca: 0.07 mass%, Sn: 1.5 mass%, the balance being impurities such as Ag and Al and Pb) was processed into a positive electrode expanded lattice by the rotary expanding method. Here, the aspect ratio of the crosspiece was changed in the range of 0.55 to 1.0, and the mass of the lattice was changed in two stages of 80% and 60% of the standard product (aspect ratio 1.0). In addition, a standard grid (conventional example) with a crossbar aspect ratio of 1.0 was manufactured. Hereinafter, the aspect ratio of the crosspiece is simply called the aspect ratio. If the Ca content is in the range of 0.05 mass% to 1.0 mass%, the Sn content is in the range of 1.0 mass% to 2.0 mass%, and the sheet thickness is in the range of 0.6 mm to 1.2 mm, the aspect ratio of the crosspiece, electrolysis On the condition that the aluminum ion content and the lithium ion content of the liquid are the same, the performance of the positive electrode plate is equivalent to that of the example. If the cross-bar aspect ratio is the same, the mass of the positive grid is approximately proportional to the square of the sheet thickness, and the grid mass increases as the sheet thickness increases.

厚さ0.8mmのPb-Ca系合金（Ca：0.09mass%，Sn：0.35mass%，残余はAg，Al等の不純物とPb）を、ロータリーエキスパンド法により負極エキスパンド格子へと加工した。桟の縦横比は0.45〜0.9の範囲で変化させ、格子の質量は標準品（縦横比0.9）の80%，60%の２段階に変化させ、他に桟の縦横比が0.9の標準品（従来例）の格子を作製した。Ca含有量が0.05mass%〜1.0mass%の範囲で、Sn含有量が0.3mass%〜1.0mass%の範囲で、シート厚が0.6mm〜1.2mmの範囲であれば、桟の縦横比、電解液のアルミニウムイオン含有量とリチウムイオン含有量とが同じであることを条件に、負極板の性能は実施例と同等になる。また桟の縦横比が同じ場合、負極格子の質量はほぼシート厚の２乗に比例する。   A 0.8 mm-thick Pb—Ca alloy (Ca: 0.09 mass%, Sn: 0.35 mass%, the remainder being impurities such as Ag and Al and Pb) was processed into a negative electrode expanded lattice by the rotary expand method. The aspect ratio of the crosspiece is changed in the range of 0.45 to 0.9, the mass of the lattice is changed in two stages of 80% and 60% of the standard product (0.9 aspect ratio), and other standard products with a crossbar aspect ratio of 0.9 ( The lattice of the conventional example) was produced. If the Ca content is in the range of 0.05 mass% to 1.0 mass%, the Sn content is in the range of 0.3 mass% to 1.0 mass%, and the sheet thickness is in the range of 0.6 mm to 1.2 mm, the cross-sectional aspect ratio, electrolysis The performance of the negative electrode plate is equivalent to that of the example, provided that the aluminum ion content and the lithium ion content of the liquid are the same. Further, when the aspect ratio of the crosspieces is the same, the mass of the negative electrode lattice is substantially proportional to the square of the sheet thickness.

正極格子、負極格子はレシプロエキスパンド法により作製しても良い。さらに格子表面層にPb-Sb系合金層、Pb-Sn系合金層等を設けても良く、特に正極格子の片面もしくは両面にPb-Sb系合金層を設けても良い。また正極格子、負極格子共に、シート厚を0.5mm未満とすると、格子展開時に桟が切れることがあった。   The positive electrode lattice and the negative electrode lattice may be produced by a reciprocating expand method. Further, a Pb—Sb alloy layer, a Pb—Sn alloy layer or the like may be provided on the lattice surface layer, and in particular, a Pb—Sb alloy layer may be provided on one surface or both surfaces of the positive electrode lattice. In addition, when the sheet thickness is less than 0.5 mm for both the positive and negative grids, the crosspieces may be cut off when the grid is developed.

ボールミル法で製造した鉛粉に合成樹脂繊維を定法に従って加え、水と希硫酸とでペースト化し、正極格子に充填後、熟成と乾燥とを施して未化成の正極板とした。同様にボールミル法で製造した鉛粉に合成樹脂繊維とリグニンとカーボンブラックと硫酸バリウムとを定法に従って加え、同様に水と希硫酸とでペースト化した。このペーストを負極格子に充填後、熟成と乾燥とを施して未化成の負極板とした。なお鉛粉の種類と含有量、活物質への添加物等は任意である。   Synthetic resin fibers were added to lead powder produced by the ball mill method in accordance with a conventional method, made into a paste with water and dilute sulfuric acid, filled into a positive electrode grid, and then subjected to aging and drying to obtain an unformed positive electrode plate. Similarly, synthetic resin fibers, lignin, carbon black, and barium sulfate were added to lead powder produced by the ball mill method according to a conventional method, and similarly, paste was formed with water and dilute sulfuric acid. After filling this paste into the negative electrode grid, aging and drying were performed to obtain an unformed negative electrode plate. In addition, the kind and content of lead powder, the additive to an active material, etc. are arbitrary.

未化成の負極板を微孔質のポリエチレンのセパレータで包み、未化成の正極板と未化成の負極板とを互い違いに積層して、同じ極性の極板の耳をストラップで接続し、未化成の極板群とした。未化成の極板群を電槽に複数セット収容し、極板群の間をセル間接続導体で接続し、電解液を注入した。電解液は20℃で比重が1.230の希硫酸にアルミニウムイオン濃度を0〜0.3mol/L、リチウムイオン濃度を0〜0.3mol/Lの範囲で変化させたものを用いた。これらのイオンは硫酸アルミニウムと硫酸リチウムの形態で添加したが、希硫酸に可溶な塩，酸化物，水酸化物等であれば添加時の形態は任意である。電解液の注入後に、定法に従い電槽化成を行い、Q-55サイズで出力12Vの鉛蓄電池とした。各試料の蓄電池は、桟の縦横比と格子の質量、アルミニウムイオン含有量、及びリチウムイオン含有量が異なる他は、共通の材料を同じ条件で処理して作製した。   Unformed negative electrode plates are wrapped in microporous polyethylene separators, unformed positive electrode plates and unformed negative electrode plates are stacked alternately, and the ears of the same polarity electrode plates are connected with straps, Electrode plate group. A plurality of unformed electrode plate groups were accommodated in a battery case, the electrode plate groups were connected by inter-cell connection conductors, and an electrolyte solution was injected. The electrolytic solution used was dilute sulfuric acid having a specific gravity of 1.230 at 20 ° C., and the aluminum ion concentration was changed in the range of 0 to 0.3 mol / L and the lithium ion concentration was changed in the range of 0 to 0.3 mol / L. These ions are added in the form of aluminum sulfate and lithium sulfate. However, the form at the time of addition is arbitrary as long as it is a salt, oxide, hydroxide or the like soluble in dilute sulfuric acid. After injecting the electrolyte, the battery was formed in accordance with a conventional method to produce a lead-acid battery of Q-55 size and 12V output. The storage batteries of each sample were produced by processing common materials under the same conditions except that the cross-bar aspect ratio and lattice mass, aluminum ion content, and lithium ion content were different.

図１〜図３に正極格子と負極格子の構造を示し、格子の構造を正極か負極かを区別せずに説明する。図１において、２は格子で、４はメッシュ部でありマス目６とその周囲の桟８とから成る。１０は上縁で、１２は耳であり極板群が互いに溶接される部分で、１４は下縁である。   1 to 3 show the structures of a positive electrode lattice and a negative electrode lattice, and the structure of the lattice will be described without distinguishing between the positive electrode and the negative electrode. In FIG. 1, 2 is a lattice, and 4 is a mesh portion, which includes a grid 6 and a bar 8 around it. Reference numeral 10 denotes an upper edge, reference numeral 12 denotes an ear, a portion where the electrode plates are welded to each other, and reference numeral 14 denotes a lower edge.

図２は桟の縦横比を示し、ｘは桟の横サイズでPb-Ca系合金シートの厚さに等しく、yは桟の縦サイズで、縦横比Aは A=y/x で与えられ、桟の長さ当たりの質量はxyに比例するので、A×x2に比例する。１６は活物質で、桟８は活物質１６の内部に埋設されている。 Figure 2 shows the aspect ratio of the crosspiece, where x is the horizontal size of the crosspiece and is equal to the thickness of the Pb-Ca alloy sheet, y is the vertical size of the crosspiece, and the aspect ratio A is given by A = y / x mass per length of the crosspiece is proportional to xy, proportional to a × x 2. Reference numeral 16 denotes an active material, and the crosspiece 8 is embedded in the active material 16.

図３にマス目６と桟８とを示し、Lはマス目６の１辺に沿った桟８の長さで、pはマス目の上下のピッチ、θは桟８が格子の横方向の基線と成す角である。マス目６の面積Sは S=4×1/2×Lsinθ×LcosSθ=L2sin2θ で与えられ、マス目６の周囲の桟８の長さは4Lなので、面積当たりの格子の質量は 4L/S に比例し、 4L/S=4L／L2sin2θなので、 4L/S=4/Lsin2θ となる。ここで p＝2Lsinθ なので、 4L/S=8/p である。格子の質量は桟の長さ当たりの質量に比例し、これはA×x2に比例するので、面積当たりの格子の質量は Ax2/Lsin2θ あるいは Ax2/pcosθに比例する。また格子の縦方向の段数は 1/p、即ち 1/Lsinθに比例し、横方向の段数は 1/Lcosθに比例する。 FIG. 3 shows the grid 6 and the crosspiece 8, where L is the length of the crosspiece 8 along one side of the grid 6, p is the vertical pitch of the grid, and θ is the crosspiece 8 in the horizontal direction of the lattice. The angle formed with the baseline. The area S of the grid 6 is given by S = 4 × 1/2 × Lsinθ × LcosSθ = L 2 sin2θ, and the length of the cross 8 around the grid 6 is 4L, so the mass of the grid per area is 4L / Since it is proportional to S and 4L / S = 4L / L 2 sin2θ, 4L / S = 4 / Lsin2θ. Here, p = 2Lsinθ, so 4L / S = 8 / p. Mass of the grating is proportional to the mass per length of the crosspiece, which is proportional to A × x 2, the mass of the lattice per area is proportional to Ax 2 / Lsin2θ or Ax 2 / pcosθ. The number of vertical steps of the lattice is 1 / p, that is, proportional to 1 / Lsinθ, and the number of horizontal steps is proportional to 1 / Lcosθ.

縦横比Aを変えても格子の質量を一定に保つため、実施例ではピッチpを縦横比Aに比例させθを固定したが、ピッチpとθの双方を変化させても良い。実施例ではθを37度としたが、例えば30度〜40度としても良い。   In order to keep the mass of the lattice constant even when the aspect ratio A is changed, the pitch p is proportional to the aspect ratio A and θ is fixed in the embodiment, but both the pitch p and θ may be changed. In the embodiment, θ is 37 degrees, but may be 30 degrees to 40 degrees, for example.

各蓄電池を３個ずつ作製し、最初にJIS D 5301:2006の9.5.3b）に規定される低温HR放電試験を行い、蓄電池の端子電圧が6Vに低下するまでの時間を測定した。次いで電池工業会規格SBA S 0101:2006の9.4.5に規定されるアイドリングストップ寿命試験を18,000サイクル行った後、蓄電池を解体して負極への硫酸鉛の蓄積量を測定した。結果は各３個の蓄電池の平均で表し、かつ標準品（表１の試料A1）での結果を100%とする相対値で表す。標準品は、桟の縦横比が正極格子で1.0、負極格子で0.9で、電解液にはアルミニウムイオンもリチウムイオンも含まない。   Three each storage battery was manufactured, and the low temperature HR discharge test prescribed | regulated to JIS D 5301: 2006 9.5.3b) was first performed, and the time until the terminal voltage of a storage battery fell to 6V was measured. Next, after performing an idling stop life test specified in 9.4.5 of Battery Industry Association Standard SBA S 0101: 2006 for 18,000 cycles, the storage battery was disassembled and the amount of lead sulfate accumulated in the negative electrode was measured. The result is expressed as an average of three storage batteries, and is expressed as a relative value with the result of a standard product (sample A1 in Table 1) as 100%. The standard product has a crossbar aspect ratio of 1.0 for the positive grid and 0.9 for the negative grid, and the electrolyte does not contain aluminum or lithium ions.

表１は正極と負極の双方で桟の縦横比を標準品から変化させた際の結果を示し、表２は正極または負極で桟の縦横比を標準品から変化させた際の結果を示す。また表１中の、アルミニウムイオンとリチウムイオンとを各0.1mol/L含有する試料での結果を図４、図５に示す。図４では格子の質量は標準格子の80%で、図５では60%である。   Table 1 shows the results when the crossbar aspect ratio was changed from the standard product for both the positive electrode and the negative electrode, and Table 2 shows the results when the crossbar aspect ratio was changed from the standard product for the positive electrode or the negative electrode. Moreover, the result in the sample containing 0.1 mol / L of aluminum ions and lithium ions in Table 1 is shown in FIGS. In FIG. 4, the mass of the grating is 80% of the standard grating and in FIG. 5 it is 60%.

Figure 0005630716
Figure 0005630716

アルミニウムイオンもリチウムイオンも含有させずに格子を軽量化すると、桟の縦横比にかかわらず、低温HR放電性能が低下し、負極への硫酸鉛の蓄積量が増す。これらの現象は、桟と活物質との接触面積が低下したことに対応するものと考えられる。これに対してアルミニウムイオンとリチウムイオンとを含有させ、縦横比を標準品よりも小さくすると、格子を軽量化しても、低温HR放電性能を向上させ、かつ負極への硫酸鉛の蓄積量を少なくできる。   If the lattice is lightened without containing aluminum ions or lithium ions, the low-temperature HR discharge performance is reduced regardless of the aspect ratio of the crosspiece, and the amount of lead sulfate accumulated on the negative electrode is increased. These phenomena are considered to correspond to a decrease in the contact area between the crosspiece and the active material. On the other hand, if aluminum ions and lithium ions are included and the aspect ratio is smaller than that of the standard product, the low-temperature HR discharge performance is improved and the amount of lead sulfate accumulated on the negative electrode is reduced even if the grid is lightened. it can.

アルミニウムイオンとリチウムイオンを含有する系で桟の縦横比を小さくすると、図４，図５から明らかなように、アイドリングストップモードでの負極への硫酸鉛の蓄積量(▲)が小さくなり、低温HR放電性能（●)も向上する。図４，図５の試料Blankはアルミニウムイオンもリチウムイオンも含有しない試料の結果を示し、(▲)と(△)との差は各0.1mol/Lのアルミニウムイオンとリチウムイオンとによる硫酸鉛の蓄積量の低下を、(●)と(○)の差は低温HR放電性能の差を表している。桟の縦横比の効果は正極板では0.85以下で増し、特に0.8以下で大きくなり、負極板では0.75以下で増し、特に0.7以下で大きくなる。   When the beam aspect ratio is reduced in a system containing aluminum ions and lithium ions, the amount of lead sulfate accumulation (▲) in the negative electrode in the idling stop mode decreases as shown in FIGS. HR discharge performance (●) is also improved. 4 and 5 show the results of the sample containing neither aluminum ion nor lithium ion, and the difference between (▲) and (△) is the difference in lead sulfate by 0.1 mol / L aluminum ion and lithium ion. The difference between (●) and (◯) represents the difference in low-temperature HR discharge performance. The effect of the aspect ratio of the crosspiece increases at 0.85 or less for the positive electrode plate, particularly increases at 0.8 or less, increases at 0.75 or less for the negative electrode plate, and particularly increases at 0.7 or less.

アルミニウムイオンの濃度が0.01mol/L（試料A9）と0.02mol/L（試料A10）とでは、負極への硫酸鉛の蓄積量に大差がある。またアルミニウムイオンの濃度を0.2mol/L（試料A12）から0.3mol/L（試料A13）へ増すと、低温HR放電性能が急激に低下する。リチウムイオンの濃度を0.01mol/L（試料A14）から0.02mol/L（試料A15）へ増すと、低温HR放電性能が著しく向上する。またリチウムイオンの濃度を0.2mol/L以上にしても（試料A16,A17）性能は向上しない。さらに標準品に対する格子の質量を80%としても60%としても、縦横比が同じでアルミニウムイオン濃度とリチウムイオン濃度が同じであれば、性能は類似である。   When the aluminum ion concentration is 0.01 mol / L (sample A9) and 0.02 mol / L (sample A10), there is a large difference in the amount of lead sulfate accumulated on the negative electrode. In addition, when the concentration of aluminum ions is increased from 0.2 mol / L (sample A12) to 0.3 mol / L (sample A13), the low-temperature HR discharge performance decreases rapidly. When the concentration of lithium ions is increased from 0.01 mol / L (sample A14) to 0.02 mol / L (sample A15), the low-temperature HR discharge performance is significantly improved. Further, even if the lithium ion concentration is 0.2 mol / L or more (samples A16 and A17), the performance is not improved. Furthermore, the performance is similar if the aspect ratio is the same and the aluminum ion concentration and lithium ion concentration are the same, regardless of whether the lattice mass relative to the standard product is 80% or 60%.

正極格子と負極格子の一方のみの縦横比を標準品から変化させた際の結果を、表２に示す。試料B1,B2はいずれも実施例で、電解液はいずれもアルミニウムイオンとリチウムイオンを各0.1mol/L含有する。   Table 2 shows the results when the aspect ratio of only one of the positive electrode lattice and the negative electrode lattice is changed from the standard product. Samples B1 and B2 are both examples, and the electrolyte solutions each contain 0.1 mol / L of aluminum ions and lithium ions.

Figure 0005630716
Figure 0005630716

実施例では桟の縦横比は格子内で一定であるが、格子の上部で大きく、下部で小さくしても良い。また電解液は硫酸とアルミニウムイオンとリチウムイオン以外に、ナトリウムイオン等を含んでいても良い。   In the embodiment, the aspect ratio of the crosspiece is constant in the lattice, but it may be large at the top of the lattice and small at the bottom. Further, the electrolytic solution may contain sodium ion or the like in addition to sulfuric acid, aluminum ion, and lithium ion.

２ 格子
４ メッシュ部
６ マス目
８ 桟
１０ 上縁
１２ 耳
１４ 下縁
１６ 活物質 2 Lattice 4 Mesh 6 Grid 8 Cross 10 Upper edge 12 Ear 14 Lower edge 16 Active material

Claims (3)

Pb-Ca系合金からなる正極格子を有する正極板と、Pb-Ca系合金からなる負極格子を有する負極板と、硫酸とアルミニウムイオンとリチウムイオンとを含む電解液とを備えている鉛蓄電池において、
前記正極格子の桟の縦横比が0.6以上0.85以下、または前記負極格子の桟の縦横比が0.5以上0.75以下で、
前記電解液はアルミニウムイオンを0.02mol/L以上0.2mol/L以下、リチウムイオンを0.02mol/L以上0.2mol/L以下含有していることを特徴とする、鉛蓄電池。 In a lead storage battery comprising a positive electrode plate having a positive electrode lattice made of a Pb-Ca alloy, a negative electrode plate having a negative electrode lattice made of a Pb-Ca alloy, and an electrolyte containing sulfuric acid, aluminum ions, and lithium ions ,
The aspect ratio of the bars of the positive grid is 0.6 or more and 0.85 or less, or the aspect ratio of the bars of the negative grid is 0.5 or more and 0.75 or less,
The lead acid battery characterized in that the electrolytic solution contains aluminum ions in an amount of 0.02 mol / L to 0.2 mol / L and lithium ions in an amount of 0.02 mol / L to 0.2 mol / L. 前記正極格子の桟の縦横比が0.6以上0.85以下、かつ、前記負極格子の桟の縦横比が0.5以上0.75以下であることを特徴とする、請求項１の鉛蓄電池。 2. The lead acid battery according to claim 1 , wherein an aspect ratio of the bars of the positive electrode lattice is 0.6 or more and 0.85 or less, and an aspect ratio of the bars of the negative electrode lattice is 0.5 or more and 0.75 or less. 前記正極格子の桟の縦横比が0.65以上0.8以下、かつ、前記負極格子の桟の縦横比が0.55以上0.7以下であることを特徴とする、請求項２の鉛蓄電池。 The lead-acid battery according to claim 2 , wherein an aspect ratio of the bars of the positive grid is 0.65 or more and 0.8 or less, and an aspect ratio of the bars of the negative grid is 0.55 or more and 0.7 or less.
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