JP4364054B2 - Lead acid battery - Google Patents
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- JP4364054B2 JP4364054B2 JP2004133435A JP2004133435A JP4364054B2 JP 4364054 B2 JP4364054 B2 JP 4364054B2 JP 2004133435 A JP2004133435 A JP 2004133435A JP 2004133435 A JP2004133435 A JP 2004133435A JP 4364054 B2 JP4364054 B2 JP 4364054B2
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- 239000002253 acid Substances 0.000 title claims description 17
- 239000000758 substrate Substances 0.000 claims description 40
- 239000011149 active material Substances 0.000 claims description 26
- 229910052787 antimony Inorganic materials 0.000 claims description 15
- 239000008151 electrolyte solution Substances 0.000 claims description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 13
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 239000002142 lead-calcium alloy Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 17
- 229910052718 tin Inorganic materials 0.000 description 14
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 239000011575 calcium Substances 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910000882 Ca alloy Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 3
- 229910001245 Sb alloy Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910006529 α-PbO Inorganic materials 0.000 description 2
- 229910000600 Ba alloy Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 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
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- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、長寿命でかつ容量回復性（回復充電時の充電受け入れ性）に優れ、特にアイドルストップシステムを採用した自動車用に好適な鉛蓄電池に関する。 The present invention relates to a lead-acid battery that has a long life and is excellent in capacity recoverability (charge acceptability during recovery charge) and that is particularly suitable for automobiles employing an idle stop system.
従来、自動車用鉛蓄電池はＳＬＩバッテリーと呼ばれるように、始動時のスターター起動、照明、イグニションに使用され、その他、高級車では１００個以上が搭載されているといわれるモーターの電源にも使用されてきた。そして前記始動時のスターター起動以外はエンジンが発電機を駆動して電力を供給するため、鉛蓄電池はさほど深い放電が行われることはなかった。また、発電機からの充電により、多くの場合は満充電状態に置かれるため、過充電に強いことが求められていた。
一方、鉛蓄電池にはメンテナンスフリー（補水無用）が求められ、その対策として正極基板に、従来のＰｂ−Ｓｂ系合金に代わって、自己放電が起き難く、電解液の減少が少ないＰｂ−Ｃａ系合金基板が用いられるようになった。
Conventionally, lead-acid batteries for automobiles are used for starter start-up, lighting, and ignition at the time of starting, called SLI batteries, and also used for the power supply of motors that are said to have more than 100 installed in high-end cars. It was. In addition to starting the starter at the time of starting, the engine drives the generator to supply electric power, so that the lead-acid battery was not discharged so deeply. Moreover, since charging from a generator often places the battery in a fully charged state, it has been required to be resistant to overcharging.
On the other hand, maintenance-free (no need for water replenishment) is required for lead-acid batteries. As a countermeasure, Pb-Ca-based materials are less likely to cause self-discharge and less decrease in electrolyte instead of conventional Pb-Sb-based alloys. Alloy substrates have been used.
しかし、近年、自動車には燃費改善や排出ガスの削減が強く求められ、それに応じてアイドリングストップシステムが導入された。前記アイドリングストップシステムは、信号待ちなどで停車中にエンジンを停止するシステムであり、前記のエンジン停止により発電機からの電力供給も停止するため、この間の電力は鉛蓄電池の放電によって賄われ、その結果、鉛蓄電池は深い充放電状態で使用されることになり、前記Ｐｂ−Ｃａ系合金基板を用いた鉛蓄電池は著しく短寿命となった。 However, in recent years, automobiles are strongly required to improve fuel consumption and reduce exhaust gas, and accordingly, an idling stop system has been introduced. The idling stop system is a system that stops the engine while stopping due to a signal, etc., and the power supply from the generator is also stopped by the engine stop, so that the power during this period is covered by the discharge of the lead storage battery, As a result, the lead storage battery is used in a deep charge / discharge state, and the lead storage battery using the Pb—Ca alloy substrate has a remarkably short life.
因みに、従来のＰｂ−Ｓｂ系合金正極基板を用いた鉛蓄電池では、基板の酸化で３価または５価のＳｂイオンが生成し、前記Ｓｂイオンは基板と活物質の界面に強固なα-ＰｂＯ２層を形成して基板と活物質間の密着性（導電性）を良好に保ち、さらに前記Ｓｂイオンは活物質に作用してその一部をゲル化し、活物質粒子間の結合力を高め、その結果深い充放電を繰り返しても活物質は軟化し難くなり、長寿命が実現される。 Incidentally, in a conventional lead storage battery using a Pb—Sb alloy positive electrode substrate, trivalent or pentavalent Sb ions are generated by oxidation of the substrate, and the Sb ions are strongly α-PbO at the interface between the substrate and the active material. Two layers are formed to maintain good adhesion (conductivity) between the substrate and the active material, and the Sb ions act on the active material to gel part of it and increase the bonding force between the active material particles. As a result, the active material is difficult to soften even after repeated deep charge and discharge, and a long life is realized.
これに対し、Ｐｂ−Ｃａ系合金正極基板では、前記Ｓｂイオンによる効果が得られないため、基板と活物質の界面が剥離し、そこへ電解液（硫酸）が侵入して硫酸鉛が生成して基板と活物質間の密着性（導電性）が低下し、そのため深い充放電を繰り返す用途では活物質粒子間の結合力が早期に低下（活物質が軟化）し、寿命がＰｂ−Ｓｂ系合金正極基板を用いた場合の半分程度になった。また放電状態で長期間放置したときは容量回復性が低下した。 On the other hand, in the Pb—Ca-based alloy positive electrode substrate, since the effect of the Sb ions cannot be obtained, the interface between the substrate and the active material is peeled off, and the electrolytic solution (sulfuric acid) enters there to produce lead sulfate. As a result, the adhesion (conductivity) between the substrate and the active material is reduced, and therefore, in applications where deep charge / discharge is repeated, the bonding force between the active material particles is reduced early (the active material is softened), and the lifetime is Pb-Sb series. It was about half of the case where an alloy positive electrode substrate was used. Moreover, the capacity recoverability decreased when left in a discharged state for a long time.
このようなことから、Ｐｂ−Ｃａ系合金正極基板の表面にＳｂを含む層を設け、或いは正極活物質にＳｂ化合物を添加して、Ｐｂ−Ｓｂ系合金正極基板を用いた場合と同様の効果を得ようとする方法（例えば、特許文献１）、或いはＳｂ以外の元素により前記Ｓｂの効果を発現させる方法（例えば、特許文献２）が提案された。 For this reason, the same effect as in the case of using a Pb—Sb alloy positive electrode substrate by providing a layer containing Sb on the surface of the Pb—Ca alloy positive electrode substrate or adding an Sb compound to the positive electrode active material. A method (for example, Patent Document 1) or a method for expressing the effect of Sb by an element other than Sb has been proposed.
一方、容量回復性の低下に対しては、電解液にアルカリ金属やアルカリ土類金属イオンを添加して電解液の比重低下を抑制する方法（例えば、特許文献３）が提案された。 On the other hand, a method for suppressing a decrease in specific gravity of an electrolytic solution by adding alkali metal or alkaline earth metal ions to the electrolytic solution has been proposed (for example, Patent Document 3).
しかし、前記方法のいずれによっても、サイクル寿命と容量回復性の両方を改善することはできなかった。 However, none of the above methods has improved both cycle life and capacity recovery.
本発明の目的は、長寿命で且つ容量回復性に優れた、正極にＰｂ−Ｃａ系合金基板を用い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 storage battery using a Pb—Ca-based alloy substrate for a positive electrode, which has a long life and excellent capacity recovery.
請求項１記載発明は、鉛−カルシウム系合金からなる正極基板表面の少なくとも一部に、または／および前記正極基板に充填された活物質にアンチモンが０．００５mass％以上０．５mass％以下含有され、さらに錫が０．００５mass％以上１．０mass％以下含有され、且つ電解液にアルミニウムが硫酸塩換算で２mass％以上５０mass％以下含有されていることを特徴とする鉛蓄電池である。 According to the first aspect of the present invention, at least a part of the surface of the positive electrode substrate made of a lead-calcium alloy and / or the active material filled in the positive electrode substrate contains 0.005 mass% to 0.5 mass% of antimony. Furthermore, it is a lead storage battery characterized in that tin is contained in an amount of 0.005 mass% to 1.0 mass% and aluminum is contained in the electrolytic solution in an amount of 2 mass% to 50 mass% in terms of sulfate.
請求項１記載発明の鉛蓄電池は、正極基板表面の少なくとも一部に、または／および正極活物質に、アンチモンを適量含有させたので、前記アンチモン（Ｓｂ）は酸化して３価または５価のＳｂイオンとなって基板と活物質の界面に強固なα-ＰｂＯ ２ 層を形成し、また基板と活物質間の密着性つまり導電性を高め、さらに前記Ｓｂイオンは活物質の一部をゲル化して活物質粒子間の結合力を高める。その他に、錫を適量含有させたので、前記錫（錫イオン）の作用により活物質粒子の導電性が高まり、前記鉛蓄電池のサイクル寿命が一層向上する。 In the lead storage battery according to the first aspect of the present invention, since an appropriate amount of antimony is contained in at least a part of the surface of the positive electrode substrate or / and the positive electrode active material, the antimony (Sb) is oxidized to be trivalent or pentavalent. It becomes Sb ions to form a strong α-PbO 2 layer at the interface between the substrate and the active material, and also improves the adhesion between the substrate and the active material, that is, the conductivity. Further, the Sb ions gel part of the active material. To increase the bonding force between the active material particles. In addition to its so was suitable amount of tin increases the conductivity of the active material particles by the action of the tin (tin ions), the cycle life of the lead-acid battery is further improved.
また請求項１記載発明の鉛蓄電池は、正極基板に耐食性および機械的性質に優れる所定組成のＰｂ−Ｃａ系合金を用いることで寿命をより良好に改善することができるものである。 The lead acid battery of claim 1, wherein the invention are those which can be better improved life Rukoto with Pb-Ca system alloy having a predetermined composition which is excellent in corrosion resistance and mechanical properties to the positive electrode substrate.
前記耐食性および機械的性質に優れるＰｂ−Ｃａ系合金としては、カルシウムを０．０２mass％以上０．０５mass％未満、錫を０．４mass％以上２．５mass％以下、アルミニウムを０．００５mass％以上０．０４mass％以下、バリウムを０．００２mass％以上０．０１４mass％以下含み、残部が鉛と不可避不純物からなるＰｂ−Ｃａ系合金、または正極基板がカルシウムを０．０２mass％以上０．０５mass％未満、錫を０．４mass％以上２．５mass％以下、アルミニウムを０．００５mass％以上０．０４mass％以下、バリウムを０．００２mass％以上０．０１４mass％以下含み、さらに銀０．００５mass％以上０．０７mass％以下、ビスマス０．０１mass％以上０．１０mass％以下、タリウム０．００１mass％以上０．０５mass％以下の群から選ばれた少なくとも１種を含み、残部が鉛と不可避不純物からなるＰｂ−Ｃａ系合金が挙げられる（特開２００３−３０６７３３号公報）。 As the Pb—Ca-based alloy having excellent corrosion resistance and mechanical properties, calcium is 0.02 mass% or more and less than 0.05 mass%, tin is 0.4 mass% or more and 2.5 mass% or less, and aluminum is 0.005 mass% or more and 0 or less. .04 mass% or less, Pb-Ca alloy containing barium in an amount of 0.002 mass% to 0.014 mass%, the balance being composed of lead and inevitable impurities, or the positive electrode substrate containing calcium in an amount of 0.02 mass% to less than 0.05 mass%, Contains 0.4 mass% to 2.5 mass% tin, 0.005 mass% to 0.04 mass% aluminum, 0.002 mass% to 0.014 mass% barium, and 0.005 mass% to 0.07 mass silver. % Or less, including at least one selected from the group of bismuth 0.01 mass% to 0.10 mass%, thallium 0.001 mass% to 0.05 mass% In addition, a Pb—Ca-based alloy whose balance is made of lead and inevitable impurities is mentioned (Japanese Patent Laid-Open No. 2003-306733).
本発明において、正極基板は、重力鋳造法、連続鋳造法、または鋳塊などを圧延加工する方法により高品質にかつ効率よく製造することができる。 In the present invention, the positive electrode substrate can be manufactured with high quality and efficiency by a gravity casting method, a continuous casting method, or a method of rolling an ingot.
本発明において、正極基板表面の少なくとも一部に、または／および活物質に含有させるアンチモンは、活物質粒子間の結合力、および活物質と基板間の密着性（導電性）を高めてサイクル寿命を改善する。また錫はイオン化して活物質の導電性を高めるのでサイクル寿命を一層向上させる。一方、電解液中に含有させるアルミニウムは正負両極に生成する硫酸鉛の可逆性を高めて長期放置後の容量回復性を改善する。 In the present invention, antimony is contained in at least part of the positive electrode substrate surface, and / or the active material, the binding force between active material particles, and the active material and cycle life by increasing the adhesion (conductivity) between the substrate To improve. Moreover, since tin ionizes and raises the electroconductivity of an active material, cycle life is further improved. On the other hand, the aluminum contained in the electrolytic solution increases the reversibility of lead sulfate produced in both the positive and negative electrodes and improves the capacity recovery after standing for a long time.
請求項１記載発明において、正極基板表面の少なくとも一部、または／および活物質に含有させるアンチモンの量を０．００５mass％以上０．５mass％以下に規定し、錫の量を０．００５mass％以上１．０mass％以下に規定する理由は、いずれが下限値未満でもまたいずれが上限値を超えても各々の効果が十分に得られず、さらに上限値を超えた場合は自己放電が起き易くなるためである。 In claim 1 the invention, at least part of the positive electrode substrate surface, or / and the amount of antimony to be contained in the active material defined below 0.005 mass% or more 0.5 mass%, more 0.005 mass% the amount of tin The reason for prescribing to 1.0 mass% or less is that any of these effects is not sufficiently obtained regardless of whether it is less than the lower limit value or exceeds the upper limit value, and if it exceeds the upper limit value, self-discharge easily occurs. Because.
本発明において、アンチモンや錫を正極活物質に含有させる方法としては、例えば、アンチモンや錫の酸化物、硫酸塩などを正極鉛粉に混合する方法が挙げられる。 In the present invention, examples of the method of incorporating antimony and tin into the positive electrode active material include a method of mixing antimony, tin oxide, sulfate, etc. with the positive electrode lead powder.
アンチモン、またはアンチモンと錫を正極基板表面の少なくとも一部に含有させる方法としては、例えば、前記アンチモンや錫を含有させた正極鉛粉を前記正極基板の少なくとも一部に層状に塗布する方法が挙げられる。 Antimony or antimony and tin in order to incorporate at least part of the positive electrode substrate surface, may, for example, a method of applying the cited positive Namariko which contains the antimony and tin in layers in at least part of the positive electrode substrate It is done.
本発明において、電解液に含有（溶解）されるアルミニウム（イオンとして存在）は、鉛蓄電池を放電状態で長期間放置したときの電解液中における硫酸イオンの濃度低下を抑制し、さらに前記アルミニウムは正極および負極に生成する硫酸鉛の結晶の粗大化または緻密化を抑制して、容量回復性を大幅に改善する。 In the present invention, aluminum contained (dissolved) in the electrolytic solution (present as ions) suppresses a decrease in the concentration of sulfate ions in the electrolytic solution when the lead storage battery is left in a discharged state for a long period of time. Capacitance recovery is greatly improved by suppressing the coarsening or densification of the lead sulfate crystals produced on the positive and negative electrodes.
本発明において、前記電解液へのアルミニウムの含有量を、硫酸塩換算で２〜５０ｇ／リットルに規定する理由は、２ｇ／リットル未満ではその効果が十分に得られず、５０ｇ／リットルを超えると電解液の導電率が低下して低温での急放電特性が低下するためである。 In the present invention, the reason why the content of aluminum in the electrolytic solution is regulated to 2 to 50 g / liter in terms of sulfate is that the effect cannot be sufficiently obtained if it is less than 2 g / liter, and the amount exceeds 50 g / liter. This is because the electrical conductivity of the electrolytic solution is lowered and the rapid discharge characteristics at low temperature are lowered.
本発明において、前記アルミニウムは、硫酸塩、炭酸塩、炭酸水素塩、リン酸塩、ホウ酸塩、水酸化物、アルミン酸塩などの硫酸水溶液や水に溶け易い化合物として電解液に添加し含有させる。 In the present invention, the aluminum is added to the electrolytic solution as a sulfuric acid aqueous solution such as sulfate, carbonate, bicarbonate, phosphate, borate, hydroxide, aluminate or a compound easily soluble in water. Let
本発明の鉛蓄電池は、特に、アイドリングストップシステム採用車、ＨＥＶ、サイクルユースなどの、深い充放電を伴う用途において長寿命化が達成されるので、鉛蓄電池の用途拡大に貢献する。 The lead-acid battery of the present invention contributes to the expansion of the use of lead-acid batteries, in particular, because a long life is achieved in applications involving deep charge / discharge, such as cars employing an idling stop system, HEV, and cycle use.
以下に本発明を実施例により詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to examples.
カルシウムを０．０４mass％、錫を１．０mass％、アルミニウムを０．０１５mass％、バリウムを０．００８mass％含有し、残部が鉛と不可避不純物からなる鉛合金をブックモールドにより毎分１５枚の速度で鋳造して正極基板を製造し、前記正極基板を１２０℃で３時間熱処理して時効硬化させた。 15 pieces per minute of lead alloy containing 0.04 mass% calcium, 1.0 mass% tin, 0.015 mass% aluminum, 0.008 mass% barium, the balance being lead and inevitable impurities A positive electrode substrate was manufactured by casting at a temperature of 120 ° C. for 3 hours and age-cured.
次に、正極用鉛粉に酸化アンチモンおよび硫酸錫を添加し混合して混合粉とし、この混合粉を常法によりペースト状物に調製し、このペースト状物を前記時効硬化後の正極基板に塗布充填し、次いで前記ペースト状物を塗布充填した正極基板を、温度４０℃、湿度９５％の雰囲気中で２４時間熟成し、乾燥して正極未化成板を作製した。前記酸化アンチモンおよび硫酸錫の添加量は種々に変化させた。 Next, antimony oxide and tin sulfate are added to the positive electrode lead powder and mixed to obtain a mixed powder. This mixed powder is prepared into a paste-like material by a conventional method, and this paste-like material is applied to the age-cured positive electrode substrate. The positive electrode substrate coated and filled, and then coated and filled with the paste-like material was aged for 24 hours in an atmosphere of a temperature of 40 ° C. and a humidity of 95%, and dried to prepare a positive electrode unformed plate. The addition amounts of the antimony oxide and tin sulfate were variously changed.
次に、前記正極未化成板の複数枚と、Ｐｂ−Ｃａ系合金からなる基板に負極活物質を塗布充填して作製した負極未化成板の複数枚とをポリエチレンセパレータを介在させて交互に積層し、この積層体の各極板をＣＯＳ方式で溶接して極板群とし、これをポリプロピレン製電槽に収容し、前記電槽内に硫酸アルミニウムを添加した電解液を注入して電槽化成を行い、５時間率容量が５０Ａｈの１２Ｖ鉛蓄電池（ＪＩＳサイズＤ２３）を製造（Ｎｏ．１〜８）した。前記硫酸アルミニウムの添加量は種々に変化させた。 Next, a plurality of positive electrode unformed plates and a plurality of negative electrode unformed plates prepared by applying and filling a negative electrode active material on a substrate made of a Pb—Ca alloy are alternately laminated with a polyethylene separator interposed therebetween. Then, each electrode plate of this laminate is welded by the COS method to form an electrode plate group, which is accommodated in a polypropylene battery case, and an electrolytic solution to which aluminum sulfate is added is injected into the battery case to form a battery case. Then, a 12V lead acid battery (JIS size D23) with a 5-hour rate capacity of 50 Ah was manufactured (No. 1 to 8) . The amount of aluminum sulfate added was varied.
得られた各々の鉛蓄電池について、サイクル寿命をＪＩＳ重負荷試験により調べた。また放電状態で６０℃×４週間放置後における容量回復性を調べた。 About each obtained lead acid battery, the cycle life was investigated by the JIS heavy load test. Further, the capacity recoverability after leaving in a discharged state at 60 ° C. for 4 weeks was examined.
正極用鉛粉に酸化アンチモンおよび硫酸錫を添加し混合して混合粉とし、この混合粉を常法によりペースト状物に調製し、このペースト状物を前記正極基板の表面に薄く塗布し、その後、前記正極用鉛粉（アンチモンおよび錫を含まず）のペースト状物を充填した他は、実施例１と同じ方法により鉛蓄電池を製造（Ｎｏ．９〜１１）し、実施例１と同じ方法によりサイクル寿命および容量回復性を調べた。 Antimony oxide and tin sulfate are added to the lead powder for the positive electrode and mixed to obtain a mixed powder. This mixed powder is prepared into a paste-like material by a conventional method, and this paste-like material is thinly applied to the surface of the positive electrode substrate. A lead-acid battery was produced by the same method as in Example 1 (Nos. 9 to 11) except that the positive electrode lead powder (not including antimony and tin) was filled, and the same method as in Example 1 Thus, cycle life and capacity recovery were examined.
比較例１として、前記Ｐｂ−Ｃａ系合金正極基板の正極活物質にＳｂおよびＳｎを含有しない他は実施例１と同じ鉛蓄電池（Ｎｏ．１２）、正極活物質にＳｂを含有しない他は実施例１と同じ鉛蓄電池（Ｎｏ．１３）、正極活物質にＳｎおよび電解液にＡｌを含有しない他は実施例１と同じ鉛蓄電池（Ｎｏ．１４）、正極活物質にＳｎを多量に含有する他は実施例１と同じ鉛蓄電池（Ｎｏ．１５）、正極活物質にＳｂを多量に含有し、Ｓｎを含有しない他は実施例１と同じ鉛蓄電池（Ｎｏ．１６）、電解液にＡｌを多量に含有する他は実施例１と同じ鉛蓄電池（Ｎｏ．１７）を製造し、実施例１と同じ方法によりサイクル寿命および容量回復性を調べた。 As Comparative Example 1, except that Sb and Sn are not contained in the positive electrode active material of the Pb—Ca-based alloy positive electrode substrate, the same lead storage battery (No. 12 ) as in Example 1, except that Sb is not contained in the positive electrode active material. example 1 the same lead-acid battery as (No.13), the same lead-acid battery (No.1 4) other containing no Al to Sn and the electrolyte in the positive electrode active material as in example 1, a large amount of S n in the positive electrode active material the same lead electric storage batteries other containing the example 1 (No. 15), large amounts contain Sb in the positive electrode active material, the same lead-acid battery (No.16) and other containing no Sn example 1, electrolytic The same lead storage battery (No. 17 ) as in Example 1 was produced except that the liquid contained a large amount of Al, and the cycle life and capacity recoverability were examined by the same method as in Example 1.
（１）サイクル寿命が１３０回以上（長寿命）、（２）容量回復性（率）が６０％以上（良好）、（３）他の電池特性に問題がない、の３条件を満足するものは総合的に優れる（○）と評価し、前記３条件のうち１つでも不満足のものがあれば総合的に劣る（×）と評価した。 (1) cycle life than 130 times (long life), (2) Capacity recovery property (index) of 6 0% or higher (good), thereby satisfying the expression (3) there is no problem in other battery characteristics, three conditions The product was evaluated as overall excellent (O), and if any one of the three conditions was unsatisfactory, it was evaluated as overall inferior (x).
実施例１〜２および比較例１の調査結果を表１に示した。 The investigation results of Examples 1 and 2 and Comparative Example 1 are shown in Table 1.
表１から明らかなように、本発明例(実施例１〜２)の鉛蓄電池（Ｎｏ．１〜１１）はいずれも長寿命であり、かつ容量回復性が良好で、他の電池特性に問題がなく、総合的に優れるものであった。前記長寿命の原因はＰｂ−Ｃａ系合金からなる正極基板表面の少なくとも一部に、または／および前記正極基板に塗布充填された活物質にアンチモン（Ｓｂ）および錫（Ｓｎ）がそれぞれ適量含有されていて、活物質粒子間の結合力が高まって活物質の軟化が防止され、また基板と活物質間の密着性（導電性）、さらに活物質の導電性が高度に維持されたためであり、容量回復性が優れた理由は電解液にアルミニウム（Ａｌ）が適量含有されていて正負両極に生成する硫酸鉛の可逆性が改善されたためである。 As is clear from Table 1, the lead storage batteries (Nos. 1 to 1 1 ) of the examples of the present invention (Examples 1 and 2 ) all have a long life, good capacity recoverability, and other battery characteristics. There was no problem and it was excellent overall. At least a portion, or / and the antimony in the active material coated filled in the positive electrode substrate (Sb) Contact Yobisuzu (Sn) is suitable amount each of the positive electrode substrate surface cause the long lifetime consisting Pb-Ca based alloy This is because the bonding force between the active material particles is increased and softening of the active material is prevented, and the adhesion (conductivity) between the substrate and the active material, and further the conductivity of the active material is maintained at a high level. The reason why the capacity recoverability is excellent is that the reversibility of lead sulfate produced in both positive and negative electrodes is improved by containing an appropriate amount of aluminum (Al) in the electrolytic solution.
これに対し、比較例１のＮｏ.１２は正極活物質にＳｂおよびＳｎが含有されていないためいずれもサイクル寿命が劣った。Ｎｏ．１３は、正極活物質にＳｂが含有されていないためサイクル寿命が劣った。Ｎｏ．１４は電解液にＡｌが含有されていないため容量回復性が劣った。Ｎｏ．１５はＳｎが多すぎたため、Ｎｏ．１６はＳｂが多すぎたためいずれも自己放電が増加した。Ｎｏ．１７は電解液にＡｌが多量に含有されたため急放電特性が低下した。このように比較例１の鉛蓄電池はいずれも総合的に劣るものであった。 On the other hand, No. 12 of Comparative Example 1 was inferior in cycle life because Sb and Sn were not contained in the positive electrode active material. No. 1 3, Sb is poor because cycle lifetime are not contained in the positive electrode active material. No. 1 4 was inferior in capacity recovery property because no Al is contained in the electrolytic solution. No. No. 15 has too much Sn. No. 16 had too much Sb, so the self discharge increased in any case. No. In No. 17, since the electrolytic solution contained a large amount of Al, the rapid discharge characteristics deteriorated. Thus, all the lead acid batteries of Comparative Example 1 were inferior overall.
実施例１〜２では、正極基板に耐食性と機械的性質に優れるＡｌ−Ｃａ−Ｓｎ−Ａｌ−Ｂａ合金を用いた例について説明したが、前記合金にさらにＡｇ、Ｂｉ、Ｔｌの群から選ばれた少なくとも1種を適量含有させた合金を用いた場合にも同様の効果が得られ、他のＡｌ−Ｃａ系合金を用いた場合にもほぼ同様の効果が得られる。 In Examples 1 and 2 , an example in which an Al—Ca—Sn—Al—Ba alloy having excellent corrosion resistance and mechanical properties was used for the positive electrode substrate was described, but the alloy was further selected from the group of Ag, Bi, and Tl. In addition, the same effect can be obtained when an alloy containing an appropriate amount of at least one kind is used, and substantially the same effect can be obtained when another Al—Ca alloy is used.
実施例１〜２では、正極基板をブックモールドを用いて製造したが、本発明は正極基板を連続鋳造法や圧延加工法など他の方法により製造した場合にも同様の効果が得られる。 In Examples 1 and 2 , the positive electrode substrate was manufactured using a book mold, but the present invention can provide the same effect when the positive electrode substrate is manufactured by other methods such as a continuous casting method and a rolling method.
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