JP2003346790A - Lead acid storage battery - Google Patents
Lead acid storage batteryInfo
- Publication number
- JP2003346790A JP2003346790A JP2002150317A JP2002150317A JP2003346790A JP 2003346790 A JP2003346790 A JP 2003346790A JP 2002150317 A JP2002150317 A JP 2002150317A JP 2002150317 A JP2002150317 A JP 2002150317A JP 2003346790 A JP2003346790 A JP 2003346790A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- mass
- positive electrode
- lead
- storage battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims abstract description 17
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000007773 negative electrode material Substances 0.000 claims abstract description 11
- 229910000882 Ca alloy Inorganic materials 0.000 claims description 5
- 238000007600 charging Methods 0.000 abstract description 14
- 229910045601 alloy Inorganic materials 0.000 abstract description 8
- 239000000956 alloy Substances 0.000 abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000011149 active material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004898 kneading Methods 0.000 description 4
- 229910014474 Ca-Sn Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000001999 grid alloy Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Cell Separators (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は鉛蓄電池に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lead storage battery.
【０００２】[0002]
【従来の技術】従来の鉛蓄電池の極板群構成として、１
セル当たりの正極板の枚数に対して負極板の枚数を１枚
多くしたものが用いられている。この理由として、負極
の枚数を正極の枚数に対して１枚増やすことで、負極の
活物質量および表面積を正極に対して余裕をもたせ、負
極の充電受入性を良好に保ちながら、蓄電池の容量低下
を抑制して寿命を維持するためである。2. Description of the Related Art A conventional lead-acid battery has a plate group consisting of
One in which the number of the negative electrode plates is increased by one with respect to the number of the positive electrode plates per cell is used. The reason for this is that by increasing the number of negative electrodes by one with respect to the number of positive electrodes, the amount of active material and the surface area of the negative electrode are given a margin with respect to the positive electrode, and the capacity of the storage battery is maintained while maintaining good charge acceptability of the negative electrode This is for suppressing the decrease and maintaining the life.
【０００３】ところが近年、蓄電池のエネルギー密度の
向上やそれによる軽量化、さらには製品の価格低減や生
産性の向上を図るために、正極と負極の枚数を同一とす
ることが行われるようになった。正極と負極の構成枚数
を同一とした場合、蓄電池の価格低減や生産性では有利
になるものの、放電量に対して充電量を削減した充放電
サイクルを繰返して行うと、蓄電池の容量が急激に低下
し、早期に寿命低下するということがわかってきた。However, in recent years, the number of positive and negative electrodes has been made the same in order to improve the energy density of the storage battery and thereby reduce the weight thereof, and further reduce the price of the product and improve the productivity. Was. When the number of components of the positive electrode and the negative electrode is the same, it is advantageous in reducing the cost and productivity of the storage battery. It has been found that the lifespan decreases early.
【０００４】従来から、車両用の鉛蓄電池では例えば１
２Ｖ鉛蓄電池の場合、充電電圧を１４．０Ｖ〜１４．５
Ｖ程度に設定することによって、蓄電池の充電状態（以
下、ＳＯＣという）をほぼ１００％に近い状態になるよ
うに制御することが行われてきた。ところが近年、車両
の燃費向上を目的として蓄電池を用いてエンジン補機類
を駆動させたり、回生出力を蓄電する制御が行われるよ
うになってきた。このような制御においては従来の車両
と異なり、ＳＯＣは１００％未満の中間状態で蓄電池が
使用される。[0004] Conventionally, lead-acid batteries for vehicles use, for example, 1
In the case of a 2V lead-acid battery, the charging voltage is from 14.0V to 14.5.
By setting the voltage to about V, the state of charge (hereinafter referred to as SOC) of the storage battery has been controlled so as to be almost 100%. However, in recent years, control for driving engine accessories and storage of regenerative output using storage batteries has been performed for the purpose of improving fuel efficiency of vehicles. In such control, unlike a conventional vehicle, the storage battery is used in an intermediate state where the SOC is less than 100%.
【０００５】このような充放電制御で正極と負極の構成
枚数が同一の鉛蓄電池を使用した場合、充電時の負極の
分極が大きくなるために、正極の充電を十分行えないま
ま充電電流が低下してしまう場合がある。このような充
放電制御を繰返して行うことで正極の充電不足によって
硫酸鉛が蓄積し、容量低下に至ると推測される。[0005] When a lead-acid battery having the same number of positive and negative electrodes is used in such charge / discharge control, the polarization of the negative electrode during charging increases, and the charging current decreases without sufficiently charging the positive electrode. In some cases. It is presumed that by repeatedly performing such charge / discharge control, lead sulfate accumulates due to insufficient charging of the positive electrode, leading to a reduction in capacity.
【０００６】また、蓄電池のメンテナンスフリー性を目
的として正極格子体としてＰｂ−Ｃａ−Ｓｎ合金を用い
た場合、従来のＰｂ−Ｓｂ系合金を用いた蓄電池に比較
して定電圧充電時の充電末期電流は低く、正極における
充電不足がさらに進行しやすいという課題があった。Further, when a Pb-Ca-Sn alloy is used as a positive electrode grid for the purpose of maintenance-free performance of a storage battery, the end of charging at the time of constant voltage charging is compared with a conventional storage battery using a Pb-Sb-based alloy. There is a problem that the current is low and insufficient charging of the positive electrode is more likely to progress.
【０００７】[0007]
【発明が解決しようとする課題】本発明は前記したよう
な特に正極と負極が同一枚数で構成される極板群を備え
た鉛蓄電池、とりわけ正極と負極とがＰｂ−Ｃａ系合金
で構成される鉛蓄電池における正極での充電不足を抑制
し、長寿命の鉛蓄電池を提供するものである。SUMMARY OF THE INVENTION The present invention relates to a lead-acid battery provided with an electrode group in which the number of positive electrodes and the number of negative electrodes are the same as described above, and in particular, the positive electrode and the negative electrode are made of a Pb-Ca alloy. It is an object of the present invention to provide a long-life lead-acid battery by suppressing insufficient charging at the positive electrode of the lead-acid battery.
【０００８】[0008]
【課題を解決するための手段】前記した課題を解決する
ために、本発明の請求項１記載に係る発明は、正極およ
び負極の格子体にＰｂ−Ｃａ系合金を用い、負極活物質
量に対して、カーボンを０．２質量％〜０．７質量％お
よび硫酸バリウムを０．５質量％〜５．０質量％添加し
た負極板を用い、セル当たりの正極板と負極板の枚数を
同数とした極板群を備えた鉛蓄電池を示すものである。In order to solve the above-mentioned problems, the invention according to claim 1 of the present invention uses a Pb-Ca-based alloy for the grid of the positive electrode and the negative electrode, and reduces the amount of the negative electrode active material. On the other hand, a negative electrode plate containing 0.2% by mass to 0.7% by mass of carbon and 0.5% by mass to 5.0% by mass of barium sulfate was used, and the number of positive electrode plates and the number of negative electrode plates per cell were the same. 1 shows a lead-acid battery provided with a group of electrode plates described above.
【０００９】また、本発明の請求項２記載に係る発明
は、請求項１記載の構成を有する鉛蓄電池において、負
極板を袋状セパレータに収納した構成を示すものであ
る。According to a second aspect of the present invention, there is provided a lead-acid battery having the configuration of the first aspect, wherein the negative electrode plate is accommodated in a bag-shaped separator.
【００１０】[0010]
【発明の実施の形態】本発明の目的は各請求項に記載し
た構成を実施の形態とすることにより達成できるのであ
るが、以下には本発明の一実施の形態における構成をそ
の構成の意義を明らかにする根拠理由と共に詳細に説明
する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The object of the present invention can be attained by implementing the constitutions described in the claims as embodiments. Hereinafter, the constitution in one embodiment of the present invention will be described. Will be described in detail together with the grounds for clarifying.
【００１１】本発明の鉛蓄電池の正極および負極の格子
体としてＰｂ−Ｃａ合金を用いる。特に正極に関しては
過放電後の回復性を勘案してＰｂ−Ｃａ−Ｓｎ合金が用
いられる。Ｐｂ−Ｃａ−Ｓｎ合金の正極格子体に正極活
物質ペーストが充填される。正極活物質ペーストとして
は、従来の一酸化鉛を主成分とする鉛粉を水もしくは水
と硫酸を添加して混練して得ることができる。また化成
効率の向上を目的として鉛粉として鉛丹を用いることが
できる。A Pb-Ca alloy is used as the grid of the positive electrode and the negative electrode of the lead storage battery of the present invention. Particularly, for the positive electrode, a Pb-Ca-Sn alloy is used in consideration of recoverability after overdischarge. A positive electrode active material paste is filled in a positive electrode lattice body of a Pb-Ca-Sn alloy. The positive electrode active material paste can be obtained by kneading a conventional lead powder mainly composed of lead monoxide by adding water or water and sulfuric acid. In addition, for the purpose of improving the formation efficiency, lead red can be used as the lead powder.
【００１２】負極格子体には負極活物質ペーストが充填
される。負極活物質ペーストは正極と同様、一酸化鉛を
主成分とする鉛粉を水もしくは水と硫酸とを添加して混
練して作製するが、鉛粉中にカーボンおよび硫酸バリウ
ムを添加する。それぞれの添加量は化成終了後の負極活
物質に対してカーボンを０．２質量％〜０．７質量％お
よび硫酸バリウムを０．５質量％〜５．０質量％とす
る。The negative electrode grid is filled with a negative electrode active material paste. Similarly to the positive electrode, the negative electrode active material paste is prepared by kneading lead powder containing lead monoxide as a main component by adding water or water and sulfuric acid, and adding carbon and barium sulfate to the lead powder. The respective amounts of addition are set to 0.2% to 0.7% by mass of carbon and 0.5% to 5.0% by mass of barium sulfate with respect to the negative electrode active material after the formation.
【００１３】カーボンと硫酸バリウムをそれぞれ０．７
質量％および５．０質量％を超えて添加しても寿命サイ
クル数の伸長はみられず、活物質ペーストの充填性が低
下するため、これ以上添加する必要はない。Each of carbon and barium sulfate is 0.7
Even if it is added in excess of 5% by mass or 5.0% by mass, the number of life cycles is not extended, and the filling property of the active material paste is reduced.
【００１４】活物質ペーストを充填した正極板および負
極板を熟成乾燥してそれぞれ未化成の正極板および負極
板とする。これら正極板と負極板の同枚数ずつをセパレ
ータを介して積層し、同極性の極板耳部同士を集合溶接
して得た極板群を作製する。セパレータとしては微孔性
ポリエチレンシートやガラス繊維を主体とするマットセ
パレータを用いることができるが、特に微孔性ポリエチ
レンシートを袋状とし、この袋状セパレータに負極板を
収納した極板群構成を用いることが好ましい。The positive electrode plate and the negative electrode plate filled with the active material paste are aged and dried to obtain unformed positive and negative electrode plates, respectively. The same number of the positive electrode plates and the same number of the negative electrode plates are laminated with a separator interposed therebetween, and an electrode plate group obtained by collectively welding electrode plate lugs having the same polarity is produced. As the separator, a microporous polyethylene sheet or a mat separator mainly composed of glass fiber can be used.In particular, the microporous polyethylene sheet is formed in a bag shape, and an electrode plate group configuration in which a negative electrode plate is stored in the bag-shaped separator is used. Preferably, it is used.
【００１５】ところで袋状セパレータに負極板を収納す
る根拠理由について述べる。負極板を袋状セパレータに
収納した蓄電池は、正極板を袋状セパレータに収納した
蓄電池に対して、蓄電池使用時の正極板膨張における袋
状セパレータの破損という問題を回避でき、負極への電
解液の拡散が阻害されることによって、負極の充電受け
入れ性が低下し、正極での充電不足が進行しやすくなる
ためである。よって袋状セパレータに負極板を収納する
のが好ましい。Now, the grounds for storing the negative electrode plate in the bag-shaped separator will be described. The storage battery in which the negative electrode plate is stored in the bag-shaped separator can avoid the problem of the bag-shaped separator being damaged by the expansion of the positive electrode plate when the storage battery is used, as compared with the storage battery in which the positive electrode plate is stored in the bag-shaped separator. This is because the diffusion of hydrogen is inhibited, the charge acceptability of the negative electrode is reduced, and the shortage of charge at the positive electrode is likely to progress. Therefore, it is preferable to store the negative electrode plate in the bag-shaped separator.
【００１６】[0016]
【実施例】本発明例および比較例による５５Ｄ２３形自
動車用鉛蓄電池（以下、電池という）を作製し、寿命特
性の比較を行った。EXAMPLE A 55D23 type lead-acid battery for automobiles (hereinafter referred to as a battery) according to the present invention and comparative example was manufactured, and the life characteristics were compared.
【００１７】正極板
本発明例および比較例の電池に用いる正極板として、Ｐ
ｂ−０．０７質量％Ｃａ−１．３ｗｔ％Ｓｎ合金を段階
的に圧廷して得た圧廷鉛シートをエキスパンド加工して
得た格子体（以下、Ｐｂ−Ｃａ正極格子という）とＰｂ
−２．４質量％Ｓｂ−０．２２質量％Ａｓ合金を鋳造し
て得た格子体（以下、Ｐｂ−Ｓｂ正極格子という）を準
備した。Positive Electrode As the positive electrode used in the batteries of the present invention and comparative examples, P
(b) A grid body (hereinafter referred to as a Pb-Ca positive grid) obtained by expanding a pressed lead sheet obtained by stepwise pressing a 0.07 mass% Ca-1.3 wt% Sn alloy, and Pb.
A grid (hereinafter referred to as a Pb-Sb positive grid) obtained by casting a -2.4 mass% Sb-0.22 mass% As alloy was prepared.
【００１８】これらのＰｂ−Ｃａ正極格子およびＰｂ−
Ｓｂ正極格子のそれぞれに一酸化鉛を７５質量％含み、
残部がＰｂ粉であるボールミル式鉛粉を水と希硫酸で混
練して得た活物質ペーストを充填し、熟成乾燥して正極
板を得た。These Pb-Ca positive electrode lattices and Pb-Ca
Each of the Sb positive grids contains 75% by weight of lead monoxide,
An active material paste obtained by kneading a ball mill type lead powder with the remainder being Pb powder with water and dilute sulfuric acid was filled, aged and dried to obtain a positive electrode plate.
【００１９】負極板
本発明例および比較例の電池に用いる負極板として、Ｐ
ｂ−０．０７質量％Ｃａ−０．２５ｗｔ％Ｓｎ合金をエ
キスパンド加工して得た格子体を準備した。この格子体
に一酸化鉛を７５質量％含み、残部がＰｂ粉であるボー
ルミル式鉛粉を水と希硫酸で混練して得た活物質ペース
トを充填し、熟成乾燥して負極板を得た。なお、本実施
例においては鉛粉に水と希硫酸とを添加する以前にカー
ボンおよび硫酸バリウムを添加した。カーボンと硫酸バ
リウムの添加量は化成終了後の負極活物質量に対してそ
れぞれ０．１質量％〜０．７質量％および０．２質量％
〜７．０質量％となるように調整した。Negative electrode plate As a negative electrode plate used in the batteries of the present invention and comparative examples, P
A lattice body obtained by expanding a b-0.07 mass% Ca-0.25 wt% Sn alloy was prepared. The grid body was filled with an active material paste obtained by kneading 75% by mass of lead monoxide and the remainder of a ball mill type lead powder composed of Pb powder with water and dilute sulfuric acid, and aged and dried to obtain a negative electrode plate. . In this example, carbon and barium sulfate were added before adding water and dilute sulfuric acid to the lead powder. The addition amounts of carbon and barium sulfate are 0.1% by mass to 0.7% by mass and 0.2% by mass with respect to the amount of the negative electrode active material after the formation.
It adjusted so that it might be -7.0 mass%.
【００２０】セパレータ
０．３ｍｍ厚の微孔性ポリエチレンシートを袋状に加工
した。A microporous polyethylene sheet having a thickness of 0.3 mm was formed into a bag.
【００２１】上記の〜で準備した正極板、負極板お
よびセパレータを用いて表１に示す構成で本発明例およ
び比較例の電池を作製した。Using the positive electrode plate, the negative electrode plate and the separator prepared in the above (1) and (2), the batteries of the present invention and comparative examples were produced with the constitution shown in Table 1.
【００２２】[0022]
【表１】 [Table 1]
【００２３】表１に示した各電池について自動車用で放
電が深く入る傾向の使われ方を想定した試験パターンで
寿命試験を行った。寿命試験条件としてＪＩＳ Ｄ５３
０１で規定する軽負荷寿命試験での４分放電−１０分充
電のサイクルを８分放電−１８分充電として行った。そ
の結果を表２に示す。なお、試験結果は表１の電池Ａ−
１の寿命サイクル数を１００とした百分率で示した。A life test was carried out for each of the batteries shown in Table 1 in a test pattern assuming that the battery was used for automobiles and the tendency of deep discharge was used. JIS D53 as life test conditions
In the light load life test specified in 01, a cycle of 4 minutes of discharge and 10 minutes of charge was performed as 8 minutes of discharge and 18 minutes of charge. Table 2 shows the results. The test results are shown in Table 1 for battery A-
The life cycle number of 1 was expressed as a percentage with 100 as the number.
【００２４】[0024]
【表２】 [Table 2]
【００２５】表２に示した結果から、正極格子を構成し
ている合金がＰｂ−Ｃａ合金であり、極板群を構成する
極板枚数が正極と負極で同一であり、特に負極がセパレ
ータに収納された電池において、負極活物質中のカーボ
ン添加量を０．２質量％〜０．７質量％、硫酸バリウム
添加量を０．５質量％〜５．０質量％とすることによ
り、深い放電を想定した寿命試験において、良好な寿命
特性を得ることができる。From the results shown in Table 2, the alloy constituting the positive electrode grid is a Pb-Ca alloy, and the number of electrodes constituting the electrode group is the same for the positive electrode and the negative electrode. In the stored battery, deep discharge is achieved by setting the amount of carbon in the negative electrode active material to 0.2% by mass to 0.7% by mass and the amount of barium sulfate to 0.5% by mass to 5.0% by mass. In the life test assuming the above, good life characteristics can be obtained.
【００２６】カーボン添加量が０．１質量％の電池Ａ−
１、Ａ−２、Ａ−３もしくは硫酸バリウム添加量が０．
２質量％である電池Ａ−１、Ｂ−１、Ｃ−１、Ｄ−１で
は正極活物質に硫酸鉛の蓄積が見られた。これらの電池
については負極の硫酸鉛の蓄積は正極ほど進行していな
いが、活物質粒子径は初期から成長し、粗大化してい
た。Battery A containing 0.1% by mass of carbon
1, A-2, A-3 or a barium sulfate addition amount of 0.
In the batteries A-1, B-1, C-1, and D-1, which were 2% by mass, accumulation of lead sulfate was observed in the positive electrode active material. In these batteries, the accumulation of lead sulfate in the negative electrode did not progress as much as in the positive electrode, but the active material particle diameter grew from the beginning and became coarse.
【００２７】これらのことから、これら比較例の電池で
は充放電が進行するにしたがい、負極活物質の表面積が
減少し、もともとの負極見かけ面積が正極５枚／負極６
枚の電池に比較して少ないこととあいまって、負極の反
応表面積が減少し、充電末期電流が減少することによっ
て、正極が充電不足になったと推測される。From these facts, in the batteries of these comparative examples, the surface area of the negative electrode active material was reduced as the charge / discharge progressed, and the original negative electrode apparent area was 5 positive electrodes / negative electrode 6
It is presumed that the positive electrode became insufficiently charged due to the decrease in the reaction surface area of the negative electrode and the decrease in the end-of-charge current, in combination with the fact that it was smaller than that of a single battery.
【００２８】一方、カーボン添加量を０．２質量％〜
０．７質量％でかつ硫酸バリウム添加量を０．５質量％
〜５．０質量％とした本発明の構成における電池Ｂ−
２、Ｂ−３、Ｃ−２、Ｃ−３、Ｅ−２については負極へ
のカーボン添加による導電性向上と、硫酸バリウムの負
極活物質の微細化による多孔質な反応表面積の増大効果
により、充放電サイクル中における負極の反応表面積の
低下を抑制することによって、正極での充電不足を抑制
したと推測される。On the other hand, when the amount of carbon added is 0.2% by mass or less.
0.7 mass% and the amount of barium sulfate added is 0.5 mass%
Battery B- in the configuration of the present invention in which
2, B-3, C-2, C-3, and E-2 are improved in conductivity by adding carbon to the negative electrode, and by increasing the porous reaction surface area by reducing the size of the negative electrode active material of barium sulfate. It is presumed that by suppressing a decrease in the reaction surface area of the negative electrode during the charge / discharge cycle, insufficient charging at the positive electrode was suppressed.
【００２９】このような本発明の効果は特に極板構成枚
数が正極と負極とで同一であって、正極格子合金がＰｂ
−Ｃａ合金で構成される電池で顕著である。正極枚数が
負極枚数よりも少ない構成である電池Ｇ−１、Ｇ−２で
は負極での反応表面積の減少が正極の充電不足にそれほ
ど影響しないからである。また、正極格子合金がＰｂ−
Ｓｂ合金で構成される電池Ｆ−１、Ｆ−２においては充
放電サイクル中に正極格子中のＳｂが負極に移行するこ
とによって負極の充電電位をより貴の方向に移行させる
ことによって充電末期電流を増大させる。この充電末期
電流の増大によってこれらの電池Ｆ−１、Ｆ−２では正
極の充電不足という本発明の課題が殆ど発生しない。The effect of the present invention is particularly effective when the number of electrode plates is the same for the positive electrode and the negative electrode, and the positive electrode grid alloy is Pb.
This is remarkable in a battery composed of a -Ca alloy. This is because in the batteries G-1 and G-2 in which the number of the positive electrodes is smaller than the number of the negative electrodes, the decrease in the reaction surface area at the negative electrode does not significantly affect the insufficient charge of the positive electrode. Further, when the positive electrode grid alloy is Pb-
In the batteries F-1 and F-2 made of an Sb alloy, Sb in the positive electrode grid shifts to the negative electrode during the charge / discharge cycle, so that the charge potential of the negative electrode shifts to a more noble direction, so that the end-of-charge current Increase. Due to the increase in the end-of-charge current, these batteries F-1 and F-2 hardly suffer from the problem of insufficient charging of the positive electrode of the present invention.
【００３０】また、正極をセパレータに収納した電池Ｅ
−１、Ｅ−２の寿命特性は負極活物質中のカーボン量、
硫酸バリウム量にそれほど影響されず安定した値を示
す。A battery E in which the positive electrode is housed in a separator
-1, E-2 life characteristics are the amount of carbon in the negative electrode active material,
It shows a stable value without being affected so much by the amount of barium sulfate.
【００３１】そして、セパレータについて特に負極をセ
パレータに収納した電池において本発明の効果をより顕
著に得ることができる。負極のセパレータへの収納は負
極への電解液の拡散を阻害し、負極の充電電位をより卑
に移行させ、充電末期電流を低下させるからである。し
たがって、本発明の効果をより顕著に得るためには負極
をセパレータに収納した電池に本発明の構成を適用する
ことが好ましい。The effect of the present invention can be more remarkably obtained particularly in a battery in which a negative electrode is accommodated in a separator. This is because the storage of the negative electrode in the separator impedes the diffusion of the electrolytic solution into the negative electrode, shifts the charging potential of the negative electrode to a more low potential, and lowers the terminal current at the end of charging. Therefore, in order to obtain the effect of the present invention more remarkably, it is preferable to apply the structure of the present invention to a battery in which the negative electrode is housed in a separator.
【００３２】[0032]
【発明の効果】以上、説明したように本発明の構成によ
ればメンテナンスフリー性を目的として正極にＰｂ−Ｃ
ａ合金を用い、材料削減による価格抑制を目的として正
極と負極の構成枚数を同一とし、さらには正極の変形に
よるセパレータ破損を避けるために負極を袋状セパレー
タに収納した構成の鉛蓄電池において、正極での充電不
足とこれに起因する寿命低下を顕著に抑制できるもので
あり、工業上、極めて有用である。As described above, according to the structure of the present invention, Pb-C
In a lead-acid battery with a configuration in which the number of components of the positive electrode and the negative electrode is the same for the purpose of controlling the price by reducing the material, and the negative electrode is housed in a bag-shaped separator to avoid separator breakage due to deformation of the positive electrode, In this case, it is possible to remarkably suppress the insufficient charging and the reduction in the life caused by the shortage, and it is extremely useful industrially.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H021 AA06 CC18 EE04 5H028 AA05 BB06 EE01 EE04 EE08 HH01 5H050 AA07 BA09 CA06 CB15 DA05 DA09 DA19 EA01 EA08 GA10 HA01 ────────────────────────────────────────────────── ─── Continuation of front page F-term (reference) 5H021 AA06 CC18 EE04 5H028 AA05 BB06 EE01 EE04 EE08 HH01 5H050 AA07 BA09 CA06 CB15 DA05 DA09 DA19 EA01 EA08 GA10 HA01
Claims (2)
合金を用い、負極活物質量に対して、カーボンを０．２
質量％〜０．７質量％および硫酸バリウムを０．５質量
％〜５．０質量％添加した負極板を用い、セル当たりの
正極板と負極板の枚数を同数とした極板群を備えたこと
を特徴とする鉛蓄電池。1. A Pb—Ca alloy is used for a grid of a positive electrode and a negative electrode, and carbon is added in an amount of 0.2 to the amount of a negative electrode active material.
A negative electrode plate to which 0.5% by mass to 0.7% by mass of barium sulfate and 0.5% by mass to 5.0% by mass of barium sulfate were added, and an electrode plate group having the same number of positive electrode plates and negative electrode plates per cell was provided. A lead-acid battery characterized by the above-mentioned.
ことを特徴とする請求項１に記載の鉛蓄電池。2. The lead-acid battery according to claim 1, wherein the negative electrode plate is housed in a bag-shaped separator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002150317A JP2003346790A (en) | 2002-05-24 | 2002-05-24 | Lead acid storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002150317A JP2003346790A (en) | 2002-05-24 | 2002-05-24 | Lead acid storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003346790A true JP2003346790A (en) | 2003-12-05 |
Family
ID=29768204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002150317A Pending JP2003346790A (en) | 2002-05-24 | 2002-05-24 | Lead acid storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003346790A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005093890A1 (en) * | 2004-03-26 | 2005-10-06 | Matsushita Electric Industrial Co., Ltd. | Lead battery and lead battery storage method |
| WO2005096431A1 (en) * | 2004-04-02 | 2005-10-13 | Matsushita Electric Industrial Co., Ltd. | Lead storage battery |
| JP2008140645A (en) * | 2006-12-01 | 2008-06-19 | Matsushita Electric Ind Co Ltd | Lead acid battery |
| JP2012074279A (en) * | 2010-09-29 | 2012-04-12 | Gs Yuasa Corp | Lead acid battery |
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| JPH09147873A (en) * | 1995-11-17 | 1997-06-06 | Japan Storage Battery Co Ltd | Negative electrode plate for lead-acid battery |
| JP2000243431A (en) * | 1999-02-19 | 2000-09-08 | Matsushita Electric Ind Co Ltd | Lead-acid battery |
| JP2001043863A (en) * | 1999-08-02 | 2001-02-16 | Shin Kobe Electric Mach Co Ltd | Sealed lead-acid battery |
| JP2001043849A (en) * | 1999-08-02 | 2001-02-16 | Shin Kobe Electric Mach Co Ltd | Sealed lead-acid battery |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60112256A (en) * | 1983-11-21 | 1985-06-18 | Shin Kobe Electric Mach Co Ltd | Negative plate for lead storage battery |
| JPH09147873A (en) * | 1995-11-17 | 1997-06-06 | Japan Storage Battery Co Ltd | Negative electrode plate for lead-acid battery |
| JP2000243431A (en) * | 1999-02-19 | 2000-09-08 | Matsushita Electric Ind Co Ltd | Lead-acid battery |
| JP2001043863A (en) * | 1999-08-02 | 2001-02-16 | Shin Kobe Electric Mach Co Ltd | Sealed lead-acid battery |
| JP2001043849A (en) * | 1999-08-02 | 2001-02-16 | Shin Kobe Electric Mach Co Ltd | Sealed lead-acid battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005093890A1 (en) * | 2004-03-26 | 2005-10-06 | Matsushita Electric Industrial Co., Ltd. | Lead battery and lead battery storage method |
| US7879490B2 (en) | 2004-03-26 | 2011-02-01 | Panasonic Corporation | Lead battery and lead battery storage method |
| WO2005096431A1 (en) * | 2004-04-02 | 2005-10-13 | Matsushita Electric Industrial Co., Ltd. | Lead storage battery |
| US8197967B2 (en) | 2004-04-02 | 2012-06-12 | Panasonic Corporation | Long life and low corrosion lead storage battery with a separator including silica and oil |
| JP2008140645A (en) * | 2006-12-01 | 2008-06-19 | Matsushita Electric Ind Co Ltd | Lead acid battery |
| JP2012074279A (en) * | 2010-09-29 | 2012-04-12 | Gs Yuasa Corp | Lead acid battery |
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