JP2019204801A - Lead-acid battery - Google Patents
Lead-acid battery Download PDFInfo
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- JP2019204801A JP2019204801A JP2019161433A JP2019161433A JP2019204801A JP 2019204801 A JP2019204801 A JP 2019204801A JP 2019161433 A JP2019161433 A JP 2019161433A JP 2019161433 A JP2019161433 A JP 2019161433A JP 2019204801 A JP2019204801 A JP 2019204801A
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- electrode plate
- battery
- lead
- negative electrode
- active material
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- 239000002253 acid Substances 0.000 title claims abstract description 11
- 239000011149 active material Substances 0.000 claims abstract description 24
- 238000003860 storage Methods 0.000 claims description 11
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- -1 polyethylene Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 229910001128 Sn alloy Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002002 slurry Substances 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
Abstract
Description
本発明は、鉛蓄電池に関するものである。 The present invention relates to a lead-acid battery.
鉛蓄電池は、信頼性、価格の安さから産業用、民生用に広く用いられており、特に自動車用鉛蓄電池（いわゆるバッテリー）の需要が多い。 Lead storage batteries are widely used for industrial use and consumer use because of their reliability and low price. In particular, there is a great demand for lead storage batteries for automobiles (so-called batteries).
近年、環境保護及び燃費改善の取り組みとして、停車時にはエンジンを停止させ、発進時に再始動するアイドリングストップスタート（以下ＩＳＳと略す）車の開発が加速されている。ＩＳＳ車に搭載さている鉛蓄電池は頻繁にエンジン始動、停止が繰り返されることにより、始動時に大電流放電回数が増え、停車中には電装品への電力供給が必要となり、放電負荷が多くなる。車両の充電はオルタネータによるが、これはエンジンを動力源としているために停車中にはスットプしてしまう。これらＩＳＳ特有の使用条件により、鉛蓄電池は完全には充電されない状態、すなわち部分充電状態（ＰＳＯＣ：Ｐａｒｔｉａｌ Ｓｔａｔｅ Ｏｆ Ｃｈａｒｇｅ）で使用される。 In recent years, as an effort to protect the environment and improve fuel efficiency, the development of an idling stop start (hereinafter abbreviated as ISS) vehicle that stops the engine when the vehicle stops and restarts the vehicle when starting is accelerated. Lead storage batteries mounted on ISS cars frequently start and stop the engine, increasing the number of large current discharges at start-up, requiring electric power to be supplied to electrical components while the car is stopped, and increasing the discharge load. The vehicle is charged by an alternator, which stops when the vehicle is stopped because the engine is used as a power source. Under these usage conditions peculiar to the ISS, the lead-acid battery is used in a state where it is not completely charged, that is, in a partially charged state (PSOC).
ＰＳＯＣ状態で鉛蓄電池を使用した場合、従来の満充電状態で使用される状況では発生しなかった問題が発生する。これは、負極格子体の集電部（耳部）が放電され、集電部の厚みが減少してしまう、いわゆる耳痩せ現象が知られている。前記耳痩せ現象が発生すると、集電部の抵抗が増加して、鉛蓄電池の充放電特性が低下し、サイクル寿命性能が低下する。 When a lead-acid battery is used in the PSOC state, a problem that does not occur in a situation where the battery is used in a conventional full charge state occurs. This is known as a so-called ear-thinning phenomenon in which the current collector (ear part) of the negative electrode grid is discharged and the thickness of the current collector decreases. When the earburn phenomenon occurs, the resistance of the current collector increases, the charge / discharge characteristics of the lead-acid battery deteriorate, and the cycle life performance deteriorates.
特許文献１では、鉛−錫合金層を負極格子体の耳部の表面に設け、かつ、満充電後における負極活物質に０．２５〜０．７５質量％のカーボンを含ませることで、耳痩せを抑制させる技術が開示されている。 In Patent Document 1, a lead-tin alloy layer is provided on the surface of the ear portion of the negative electrode lattice body, and the negative electrode active material after full charge is contained in an amount of 0.25 to 0.75% by mass of carbon. A technique for suppressing skinnyness is disclosed.
負極板は、負極格子体に活物質ペーストを充填して作製される。前記活物質ペーストは、鉛粉に有機添加剤、カーボン、硫酸バリウムを混合し、水及び希硫酸を添加、混練して作製される。カーボンあるいは炭素材は、導電補助剤として添加されている。 The negative electrode plate is produced by filling an active material paste into a negative electrode grid. The active material paste is prepared by mixing an organic additive, carbon, and barium sulfate with lead powder, adding water and dilute sulfuric acid, and kneading. Carbon or a carbon material is added as a conductive auxiliary agent.
通常、鉛蓄電池において、満充電後における負極活物質に対して、カーボンは０．１〜０．３質量％含まれている。０．５質量％以上カーボン量を増やすと活物質ペーストが固くなり、負極格子体への充填がしにくくなり、充填不良が発生し歩留りが低下する。 Usually, in a lead storage battery, 0.1 to 0.3 mass% of carbon is contained with respect to the negative electrode active material after full charge. When the amount of carbon is increased by 0.5% by mass or more, the active material paste becomes hard, it becomes difficult to fill the negative electrode lattice body, filling failure occurs, and the yield decreases.
活物質ペーストを適正な固さにするために、前記混練時に加える水の量を増やし、水分量を多くする方法がある。しかし、ペースト水分量を増やした負極板は、充填後の熟成、乾燥工程で水分が抜けることで活物質が収縮し、負極板表面に亀裂が生じる。このような状態では、続く電池の組み立て工程において、活物質の脱落が生じることになる。従って、ペースト水分量を増やすことは好ましくない。 In order to make the active material paste have an appropriate hardness, there is a method of increasing the amount of water by increasing the amount of water added during the kneading. However, in the negative electrode plate with an increased amount of paste water, the active material shrinks due to the release of water in the aging and drying steps after filling, and cracks occur on the surface of the negative electrode plate. In such a state, the active material falls off in the subsequent battery assembly process. Therefore, it is not preferable to increase the paste water content.
本発明の目的は、ペースト仕様を変えることなく、負極集電部の耳痩せを緩和することである。 An object of the present invention is to alleviate the ear burn of the negative electrode current collector without changing the paste specifications.
そこで本発明は、上記課題を解決するために以下の構成とする。 Therefore, the present invention has the following configuration in order to solve the above problems.
第１の発明は、セパレータを介して正極板と負極板を交互に積層した極板群を電槽に収納する鉛蓄電池において、前記正極板の総表面積をＳ、前記極板群の体積をＶとしたとき、Ｓ／Ｖが３．９５ｃｍ−１以上であり、かつ、前記正極板の活物質量をＸ、前記負極板の活物質量をＹとしたとき、Ｘ／Ｙが１．３５以上とする。 1st invention WHEREIN: In the lead storage battery which accommodates the electrode group which laminated | stacked the positive electrode plate and the negative electrode plate alternately via the separator in a battery case, the total surface area of the said positive electrode plate is set to S, and the volume of the said electrode plate group is set to V. When the S / V is 3.95 cm −1 or more, the active material amount of the positive electrode plate is X, and the active material amount of the negative electrode plate is Y, X / Y is 1.35 or more. And
第２の発明は、第１の発明において、Ｓ／Ｖが４．２ｃｍ−１以上であり、かつ、Ｘ／Ｙが１．４５以上とする。 According to a second invention, in the first invention, S / V is 4.2 cm −1 or more and X / Y is 1.45 or more.
本発明によれば、ペースト仕様を変えることなく、負極集電部の耳痩せを緩和することができ、サイクル寿命特性に優れた鉛蓄電池を得ることができる。 According to the present invention, it is possible to relieve the earring of the negative electrode current collector without changing the paste specifications, and it is possible to obtain a lead storage battery having excellent cycle life characteristics.
以下、図面を参照して本発明の好ましい実施形態を詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.
（格子体）
格子体は、鉛−カルシウム−スズ系合金シートに切れ目をいれて拡開した図２に示すエキスパンド格子体１を用いた。集電部２を除いた寸法は、正極用が幅１４５ｍｍ、高さ１１５ｍｍ、厚さ１．５ｍｍ、負極用が幅１４５ｍｍ、高さ１１５ｍｍ、厚さ１．３ｍｍである。なお、集電部２は耳部とも呼ばれる。
(Lattice)
As the lattice body, the expanded lattice body 1 shown in FIG. 2, which was expanded by cutting a lead-calcium-tin alloy sheet, was used. The dimensions excluding the current collector 2 are 145 mm wide, 115 mm high, and 1.5 mm thick for the positive electrode, and 145 mm wide, 115 mm high, and 1.3 mm thick for the negative electrode. The current collector 2 is also called an ear.
（正極板）
ボールミル法によって作製した酸化度７０％の鉛粉に、鉛丹化度９０％の鉛丹を希硫酸と混合・反応させたスラリと水および希硫酸を加えて混練し、活物質ペーストを作製する。この活物質ペーストを、前記正極用エキスパンド格子体１に充填し、常法により熟成・乾燥後に、図３に示す正極板３を得る。図２において、活物質ペーストを充填した部分が充填部４である。
(Positive electrode plate)
An active material paste is prepared by adding slurry and water and dilute sulfuric acid prepared by mixing and reacting lead tan with a lead oxidation degree of 90% to dilute sulfuric acid to lead powder with an oxidation degree of 70% produced by the ball mill method. . The active material paste is filled into the positive electrode expanded lattice 1 and after aging and drying by a conventional method, the positive electrode plate 3 shown in FIG. 3 is obtained. In FIG. 2, the portion filled with the active material paste is a filling portion 4.
（負極板）
ボールミル法によって作製した酸化度７０％の鉛粉に、添加剤として、炭素粉末、リグニン粉末、バリウム化合物粉末を加え混合する。続いて、水および希硫酸を加えて混練し、活物質ペーストを作製する。この活物質ペーストを、前記負極用エキスパンド格子体に充填し、常法により熟成・乾燥して負極板とする。
(Negative electrode plate)
Carbon powder, lignin powder, and barium compound powder are added and mixed as additives to lead powder having a degree of oxidation of 70% produced by the ball mill method. Subsequently, water and dilute sulfuric acid are added and kneaded to prepare an active material paste. The active material paste is filled into the negative electrode expanded lattice and aged and dried by a conventional method to form a negative electrode plate.
（袋セパレータ）
図４に微多孔性のポリエチレン製シート６を示す。ポリエチレン製シート６の片面には、長手方向にセパレータのリブ７が設けられており、ポリエチレン製シート６のベース部の厚みは０．２ｍｍ、リブ７を含めた総厚みは０．８ｍｍである。ポリエチレン製シート６を長さ２３５ｍｍ、幅１５２ｍｍに切り出し二つ折りにする。続いて両側部をメカニカルシール、又は熱溶着し、図５のような袋セパレータ８に加工する。
(Bag separator)
FIG. 4 shows a microporous polyethylene sheet 6. A separator rib 7 is provided on one side of the polyethylene sheet 6 in the longitudinal direction. The thickness of the base portion of the polyethylene sheet 6 is 0.2 mm, and the total thickness including the rib 7 is 0.8 mm. The polyethylene sheet 6 is cut into a length of 235 mm and a width of 152 mm and folded in half. Subsequently, both sides are mechanically sealed or heat-welded and processed into a bag separator 8 as shown in FIG.
（ストラップ形成と極板群）
図５に示すように、前記袋セパレータ８に負極板５を入れ、正極板７枚と袋セパレータに包まれた負極板８枚を交互に積層する。正極、負極それぞれの集電部２をキャストオンストラップ（Ｃａｓｔ Ｏｎ Ｓｔｒａｐ）法で溶接し、図１に示す溶接部、すなわちストラップ９を形成させ、極板群１０を得る。
なお、ストラップ９の合金組成としては、鉛−アンチモン系合金または鉛−スズ系合金を用いることができる。
(Strap formation and electrode plate group)
As shown in FIG. 5, the negative electrode plate 5 is put in the bag separator 8, and the seven positive electrode plates and the eight negative electrode plates wrapped in the bag separator are alternately laminated. The current collector 2 of each of the positive electrode and the negative electrode is welded by a cast on strap method to form a welded portion, that is, a strap 9 shown in FIG.
As the alloy composition of the strap 9, a lead-antimony alloy or a lead-tin alloy can be used.
（電槽）
図６にポリプロピレン製の電槽１１を示す。電槽１１は、隔壁１２によって６区画に分割され、セル室１３を設けられる。前記極板群１０は別名単電池といい、これは２Ｖの電池能力しかない。自動車用の電装品は、直流電圧１２Ｖを昇圧または降圧して駆動するため、極板群１０を６個直列接続して、２Ｖ×６＝１２Ｖとしている。そのため、セル室１３は６個必要である。
電槽１１の隔壁１２の両面及び電槽１１の両端面の内壁面に、リブ１４が電槽１１の高さ方向に複数本設けられている。リブ１４は、極板群を適切に加圧する役割がある。
(Battery case)
FIG. 6 shows a battery case 11 made of polypropylene. The battery case 11 is divided into six sections by a partition wall 12 and a cell chamber 13 is provided. The electrode plate group 10 is also called a single cell, which has only a battery capacity of 2V. In order to drive an electric component for automobiles by stepping up or down a DC voltage of 12V, six electrode plate groups 10 are connected in series to be 2V × 6 = 12V. Therefore, six cell chambers 13 are required.
A plurality of ribs 14 are provided in the height direction of the battery case 11 on both surfaces of the partition wall 12 of the battery case 11 and inner wall surfaces of both end surfaces of the battery case 11. The rib 14 has a role of appropriately pressing the electrode plate group.
（電池の作製）
前記極板群１０を電槽１１のセル室１３に挿入し、隣あう極板群同士のストラップ９を隔壁貫通溶接で溶接する。前記電槽１１にポリプロピレン製の蓋１５を熱溶着し、図７に示す電池１６を作製する。なお、図７に示す両端のセル室に収納する極板群１０には、ストラップ９に柱状部分を付与した極柱を形成する。これは、蓋１５に突設された正極端子１７Ａおよび負極端子１７Ｂに接続させるためのものである。
(Production of battery)
The electrode plate group 10 is inserted into the cell chamber 13 of the battery case 11, and the straps 9 between adjacent electrode plate groups are welded by partition wall welding. A polypropylene lid 15 is thermally welded to the battery case 11 to produce a battery 16 shown in FIG. In the electrode plate group 10 accommodated in the cell chambers at both ends shown in FIG. This is for connection to the positive terminal 17A and the negative terminal 17B protruding from the lid 15.
続いて、蓋１５のセル室１３に対応した注液口１８から電解液である希硫酸を注液し、周囲温度４０℃、電流２５Ａで２０時間通電して電槽化成する。電槽化成後、電解液液面を調整し、ＪＩＳＤ５３０１規定の８０Ｄ２３形電池を作製した。 Subsequently, dilute sulfuric acid, which is an electrolytic solution, is injected from the injection port 18 corresponding to the cell chamber 13 of the lid 15 and energized for 20 hours at an ambient temperature of 40 ° C. and a current of 25 A to form a battery case. After the formation of the battery case, the electrolyte solution level was adjusted to produce an 80D23 type battery defined by JIS D5301.
（正極板の総表面積、極板群の体積）
正極板３の総表面積とは、鉛蓄電池の最小単位である単電池、すなわち前記セル室１３内に収容される極板群１０において、この中の正極板３の発電に関与する部分の表面積の合計である。これは、図３において、各正極板の集電部２および活物質ペーストの未充填部を除いた部分の表と裏両面の表面積の合計に、極板群１０を構成する正極板の枚数を乗じたものである。
すなわち、極板群１０当たりの正極板の総表面積Ｓは、図３から（数１）で与えられる。なお、本発明では、Ｓの単位として〔ｃｍ２〕を用いる。
Ｓ＝（充填部幅×充填部高さ）×２×正極板枚数・・・（数１）
極板群１０の体積とは、鉛蓄電池の最小単位である１セル内に収容される極板群の各部のうち、集電部２およびストラップ９を含まない部分で、袋セパレータ８の極板に当接していないはみ出し部分と極板群１０の両端面のリブ７の高さを含む外形寸法から計算される見かけの体積である。
(Total surface area of positive electrode plate, volume of electrode plate group)
The total surface area of the positive electrode plate 3 is the surface area of the portion of the positive electrode plate 3 involved in power generation in the unit cell that is the smallest unit of the lead storage battery, that is, the electrode plate group 10 accommodated in the cell chamber 13. Total. In FIG. 3, the total number of the surface areas of the front and back surfaces of the positive electrode plates excluding the current collecting part 2 and the unfilled part of the active material paste is the number of positive electrode plates constituting the electrode group 10. It is multiplied.
That is, the total surface area S of the positive electrode plate per electrode plate group 10 is given by (Equation 1) from FIG. In the present invention, [cm 2 ] is used as a unit of S.
S = (filling portion width × filling portion height) × 2 × number of positive electrode plates (Equation 1)
The volume of the electrode plate group 10 is a portion of the electrode plate group accommodated in one cell, which is the minimum unit of the lead storage battery, and does not include the current collector 2 and the strap 9. This is the apparent volume calculated from the external dimensions including the protruding portion not in contact with the rib and the height of the ribs 7 on both end faces of the electrode plate group 10.
すなわち、極板群１０の体積Ｖは、図１から（数２）で与えられる。なお、本発明では、Ｖの単位として〔ｃｍ３〕を用いる。
Ｖ＝極板群幅×極板群厚さ×極板群高さ・・・（数２）
That is, the volume V of the electrode plate group 10 is given by (Equation 2) from FIG. In the present invention, [cm 3 ] is used as a unit of V.
V = electrode group width × electrode group thickness × electrode group height (Equation 2)
（活物質量）
活物質量とは、電槽化成後の活物質の総量で、極板総質量から格子体総質量を引いた値である。
(Amount of active material)
The amount of active material is the total amount of active material after battery case formation, and is a value obtained by subtracting the total mass of the grid from the total mass of the electrode plates.
すなわち、正極活物質量は、１枚の正極板３の活物質量に、極板群１０を構成する正極板の枚数を乗じたものである。負極活物質量は、１枚の負極板４の活物質量に、極板群１０を構成する負極板の枚数を乗じたものである。 That is, the positive electrode active material amount is obtained by multiplying the active material amount of one positive electrode plate 3 by the number of positive electrode plates constituting the electrode plate group 10. The amount of negative electrode active material is obtained by multiplying the amount of active material of one negative electrode plate 4 by the number of negative electrode plates constituting the electrode plate group 10.
（評価試験）
前記電池に２５℃環境下で以下の試験を実施する。
（ア）電流５９Ａで５９秒間定電流放電。
（イ）電流３００Ａで１秒間定電流放電。
（ウ）定電圧１４．０Ｖ、制限電流１００Ａで１分間定電流・定電圧充電。
（エ）（ア）から（ウ）を１サイクルとして充放電を繰り返す。
電池の寿命判定は、（イ）の１秒目電流が７．２Ｖ以下となったときとする。
(Evaluation test)
The following tests are performed on the battery in a 25 ° C. environment.
(A) Constant current discharge at a current of 59 A for 59 seconds.
(A) Constant current discharge at a current of 300 A for 1 second.
(C) Constant current / constant voltage charging at a constant voltage of 14.0 V and a limiting current of 100 A for 1 minute.
(D) Charging / discharging is repeated with (a) to (c) as one cycle.
The battery life is determined when the first-second current in (b) becomes 7.2 V or less.
以下、本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
（実施例１）
前記８０Ｄ２３形電池において、Ｓ／Ｖが以下のようになるように作製した。
（数１）から、Ｓ＝（１４．５×１１）×２×７＝２２３３〔ｃｍ２〕
（数２）から、Ｖ＝１４．５×３.３６×１１.６＝５６５〔ｃｍ３〕
従って、Ｓ／Ｖは３．９５ｃｍ−１となる。
Ｘ／Ｙは１．３５になるように作製した。
Example 1
In the 80D23 type battery, S / V was produced as follows.
From (Equation 1), S = (14.5 × 11) × 2 × 7 = 2233 [cm 2 ]
From (Equation 2), V = 14.5 × 3.36 × 11.6 = 565 [cm 3 ]
Therefore, S / V is 3.95 cm −1 .
X / Y was made to be 1.35.
（実施例２）
実施例１において、Ｓ／Ｖが３．９５ｃｍ−１であり、Ｘ／Ｙは１．４となる電池を作製した。
(Example 2)
In Example 1, a battery having S / V of 3.95 cm −1 and X / Y of 1.4 was produced.
（実施例３）
実施例１において、Ｓ／Ｖが３．９５ｃｍ−１であり、Ｘ／Ｙは１．４５となる電池を作製した。
Example 3
In Example 1, a battery having S / V of 3.95 cm −1 and X / Y of 1.45 was produced.
（実施例４）
実施例１において、Ｓ／Ｖが３．９５ｃｍ−１であり、Ｘ／Ｙは１．４７となる電池を作製した。
Example 4
In Example 1, a battery having S / V of 3.95 cm −1 and X / Y of 1.47 was manufactured.
（実施例５）
実施例１において、Ｓ／Ｖが４．１ｃｍ−１であり、Ｘ／Ｙは１．３５となる電池を作製した。
(Example 5)
In Example 1, a battery having S / V of 4.1 cm −1 and X / Y of 1.35 was produced.
（実施例６）
実施例１において、Ｓ／Ｖが４．１ｃｍ−１であり、Ｘ／Ｙは１．４となる電池を作製した。
(Example 6)
In Example 1, a battery having S / V of 4.1 cm −1 and X / Y of 1.4 was produced.
（実施例７）
実施例１において、Ｓ／Ｖが４．１ｃｍ−１であり、Ｘ／Ｙは１．４５となる電池を作製した。
(Example 7)
In Example 1, a battery having S / V of 4.1 cm −1 and X / Y of 1.45 was manufactured.
（実施例８）
実施例１において、Ｓ／Ｖが４．１ｃｍ−１であり、Ｘ／Ｙは１．４７となる電池を作製した。
(Example 8)
In Example 1, a battery having S / V of 4.1 cm −1 and X / Y of 1.47 was manufactured.
（実施例９）
実施例１において、Ｓ／Ｖが４．２ｃｍ−１であり、Ｘ／Ｙは１．３５となる電池を作製した。
Example 9
In Example 1, a battery having S / V of 4.2 cm −1 and X / Y of 1.35 was produced.
（実施例１０）
実施例１において、Ｓ／Ｖが４．２ｃｍ−１であり、Ｘ／Ｙは１．４となる電池を作製した。
(Example 10)
In Example 1, a battery having S / V of 4.2 cm −1 and X / Y of 1.4 was produced.
（実施例１１）
実施例１において、Ｓ／Ｖが４．２ｃｍ−１であり、Ｘ／Ｙは１．４５となる電池を作製した。
(Example 11)
In Example 1, a battery having S / V of 4.2 cm −1 and X / Y of 1.45 was produced.
（実施例１２）
実施例１において、Ｓ／Ｖが４．２ｃｍ−１であり、Ｘ／Ｙは１．４７となる電池を作製した。
(Example 12)
In Example 1, a battery having S / V of 4.2 cm −1 and X / Y of 1.47 was manufactured.
（実施例１３）
実施例１において、Ｓ／Ｖが４．３ｃｍ−１であり、Ｘ／Ｙは１．３５となる電池を作製した。
(Example 13)
In Example 1, a battery having S / V of 4.3 cm −1 and X / Y of 1.35 was produced.
（実施例１４）
実施例１において、Ｓ／Ｖが４．３ｃｍ−１であり、Ｘ／Ｙは１．４となる電池を作製した。
(Example 14)
In Example 1, a battery having S / V of 4.3 cm −1 and X / Y of 1.4 was produced.
（実施例１５）
実施例１において、Ｓ／Ｖが４．３ｃｍ−１であり、Ｘ／Ｙは１．４５となる電池を作製した。
(Example 15)
In Example 1, a battery having S / V of 4.3 cm −1 and X / Y of 1.45 was manufactured.
（実施例１６）
実施例１において、Ｓ／Ｖが４．３ｃｍ−１であり、Ｘ／Ｙは１．４７となる電池を作製した。
(Example 16)
In Example 1, a battery having S / V of 4.3 cm −1 and X / Y of 1.47 was manufactured.
（比較例１）
実施例１において、Ｓ／Ｖが３．９５ｃｍ−１であり、Ｘ／Ｙは１．３３となる電池を作製した。
(Comparative Example 1)
In Example 1, a battery having S / V of 3.95 cm −1 and X / Y of 1.33 was produced.
（比較例２）
実施例１において、Ｓ／Ｖが４．１ｃｍ−１であり、Ｘ／Ｙは１．３３となる電池を作製した。
(Comparative Example 2)
In Example 1, a battery having S / V of 4.1 cm −1 and X / Y of 1.33 was produced.
（比較例３）
実施例１において、Ｓ／Ｖが４．２ｃｍ−１であり、Ｘ／Ｙは１．３３となる電池を作製した。
(Comparative Example 3)
In Example 1, a battery having S / V of 4.2 cm −1 and X / Y of 1.33 was produced.
（比較例４）
実施例１において、Ｓ／Ｖが４．３ｃｍ−１であり、Ｘ／Ｙは１．３３となる電池を作製した。
(Comparative Example 4)
In Example 1, a battery having S / V of 4.3 cm −1 and X / Y of 1.33 was produced.
（比較例５）
実施例１において、Ｓ／Ｖが３．９ｃｍ−１であり、Ｘ／Ｙは１．３５となる電池を作製した。
(Comparative Example 5)
In Example 1, a battery having S / V of 3.9 cm −1 and X / Y of 1.35 was produced.
（比較例６）
実施例１において、Ｓ／Ｖが３．９ｃｍ−１であり、Ｘ／Ｙは１．４となる電池を作製した。
(Comparative Example 6)
In Example 1, a battery having S / V of 3.9 cm −1 and X / Y of 1.4 was produced.
（比較例７）
実施例１において、Ｓ／Ｖが３．９ｃｍ−１であり、Ｘ／Ｙは１．４５となる電池を作製した。
(Comparative Example 7)
In Example 1, a battery having S / V of 3.9 cm −1 and X / Y of 1.45 was produced.
（比較例８）
実施例１において、Ｓ／Ｖが３．９ｃｍ−１であり、Ｘ／Ｙは１．４７となる電池を作製した。
(Comparative Example 8)
In Example 1, a battery having S / V of 3.9 cm −1 and X / Y of 1.47 was manufactured.
（比較例９）
実施例１において、Ｓ／Ｖが３．９ｃｍ−１であり、Ｘ／Ｙは１．３３となる電池を作製した。
(Comparative Example 9)
In Example 1, a battery having S / V of 3.9 cm −1 and X / Y of 1.33 was produced.
表１に、これらの鉛蓄電池の寿命試験を行ったときのサイクル数の結果を示す。 Table 1 shows the results of the number of cycles when performing a life test of these lead storage batteries.
本発明を用いた実施例１〜１６は、寿命サイクル数が優れることが分かる。寿命モードを検証するため、比較例９の寿命サイクル数で各電池を解体したところ、集電部（耳部）の厚みは比較例９が最も薄く、実施例１１、１２、１５、１６が最も厚かった。これより、本実施例では、負極集電部の耳痩せを緩和することができ、サイクル寿命特性が向上したといえる。 It turns out that Examples 1-16 using this invention are excellent in the number of life cycles. In order to verify the life mode, when each battery was disassembled with the life cycle number of Comparative Example 9, the thickness of the current collector (ear part) was the smallest in Comparative Example 9, and Examples 11, 12, 15, and 16 were the most. It was thick. From this, it can be said that in this example, it was possible to relieve the earring of the negative electrode current collector, and the cycle life characteristics were improved.
これらの理由は、定かではないが極板群体積に対する正極板の総表面積の比率（Ｓ／Ｖ）が３．９５ｃｍ−１以上であることで充電時の過電圧の上昇を緩やかにしたと考えられる。また、負極活物質に対する正極活物質の比率（Ｘ／Ｙ）を１．３５以上とすることで、負極耳部で生成した硫酸鉛が完全に金属鉛に還元されるためであると考えられる。特に、正極板の表面積が増えることで抵抗が減少し、より過電圧が低下すると考えられるので、Ｓ／Ｖが４．２ｃｍ−１以上にあると好ましい。また、正極の活物質量が増えることでより負極が充分卑な電位で還元されるためであると考えられるので、Ｘ／Ｙが１．４５以上にあると好ましい。 Although it is not clear, it is considered that the ratio of the total surface area of the positive electrode plate to the electrode group volume (S / V) is 3.95 cm −1 or more, which moderates the increase in overvoltage during charging. . Moreover, it is considered that the ratio of the positive electrode active material to the negative electrode active material (X / Y) is 1.35 or more, so that lead sulfate generated at the negative electrode ear is completely reduced to metallic lead. In particular, it is considered that when the surface area of the positive electrode plate is increased, the resistance is decreased and the overvoltage is further lowered. Therefore, the S / V is preferably 4.2 cm −1 or more. Further, since it is considered that the negative electrode is reduced at a sufficiently low potential by increasing the amount of the active material of the positive electrode, X / Y is preferably 1.45 or more.
なお、本発明において上限値を規定していないが、鉛蓄電池の実用上、Ｓ／Ｖの上限は５．２ｃｍ−１、Ｘ／Ｙの上限は１．６が好ましい。 In addition, although the upper limit is not prescribed | regulated in this invention, the upper limit of S / V is 5.2 cm < -1 > and the upper limit of X / Y is 1.6 for the practical use of lead acid battery.
なお、本発明においてはＳ／Ｖの上限値を規定していないが、鉛蓄電池の実用上、上限は５．２ｃｍ−１が好ましい。 In addition, although the upper limit of S / V is not prescribed | regulated in this invention, 5.2 cm < -1 > is preferable on the practical use of a lead storage battery.
上記実施例において、極板の厚みを調整してＳ／Ｖを変えたが、エキスパンド格子体１の厚み、ポリエチレン製シート６のベース厚み、リブ７の高さを変えることによってもＳ／Ｖを変えることもできる。 In the above embodiment, the S / V was changed by adjusting the thickness of the electrode plate. However, the S / V was also changed by changing the thickness of the expanded grid 1, the base thickness of the polyethylene sheet 6, and the height of the rib 7. It can also be changed.
１．エキスパンド格子体、２．集電部、３．正極板、４．充填部、５．負極板、６．ポリエチレン製シート、７．リブ、８．袋セパレータ、９．ストラップ、１０．極板群、１１．電槽、１２．隔壁、１３．セル室、１４．リブ、１５．蓋、１６．電池、１７Ａ．正極端子、１７Ｂ．負極端子、１８．注液口。
1. Expanded lattice, 2. 2. current collector; Positive electrode plate, 4. Filling section, 5. Negative electrode plate, 6. 6. a polyethylene sheet; Ribs, 8. Bag separator, 9. Strap, 10. 10. Electrode plate group, Battery case, 12. Partition, 13. Cell chamber, 14. Ribs, 15. Lid, 16. Battery, 17A. Positive terminal, 17B. Negative electrode terminal, 18. Injection port.
Claims (2)
The lead acid battery according to claim 1, wherein S / V is 4.2 cm -1 or more and X / Y is 1.45 or more.
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