JP2006210059A - Lead acid storage battery - Google Patents
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- JP2006210059A JP2006210059A JP2005018571A JP2005018571A JP2006210059A JP 2006210059 A JP2006210059 A JP 2006210059A JP 2005018571 A JP2005018571 A JP 2005018571A JP 2005018571 A JP2005018571 A JP 2005018571A JP 2006210059 A JP2006210059 A JP 2006210059A
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- 239000002253 acid Substances 0.000 title claims abstract description 12
- 238000003860 storage Methods 0.000 title abstract description 15
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 22
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 19
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 229910000978 Pb alloy Inorganic materials 0.000 claims abstract description 10
- 239000011575 calcium Substances 0.000 claims abstract description 9
- 239000007774 positive electrode material Substances 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- -1 aluminum ions Chemical class 0.000 claims description 7
- 239000011149 active material Substances 0.000 abstract description 18
- 239000007788 liquid Substances 0.000 abstract 1
- 238000002161 passivation Methods 0.000 abstract 1
- 239000008151 electrolyte solution Substances 0.000 description 12
- 238000011084 recovery Methods 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002003 electrode paste Substances 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910018725 Sn—Al Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XPDICGYEJXYUDW-UHFFFAOYSA-N tetraarsenic tetrasulfide Chemical compound S1[As]2S[As]3[As]1S[As]2S3 XPDICGYEJXYUDW-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910006529 α-PbO 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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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
本発明は鉛蓄電池の寿命延長並びに放電状態での放置後の容量回復性、特に正極が改善された蓄電池に関するものである。 The present invention relates to a storage battery in which the life of a lead storage battery is extended and the capacity is recovered after being left in a discharged state, in particular, the positive electrode is improved.
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、始動時のスタータ起動、照明、イグニションをはじめ、高級車では１００個以上搭載されていると言うモーターの電源として使用されてきたが、始動時のスタータ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。同時に、過充電時のガス発生による電解液の減少を抑制し、補水の手間をなくすメンテナンスフリー性が求められ、正極基板合金はＰｂ−Ｓｂ系からＰｂ−Ｃａ系に変更された。 Conventionally, lead-acid batteries for automobiles have been used as a power source for motors that are installed in more than 100 high-end cars, including starter start-up, lighting, ignition, etc. Since the engine drives the generator and supplies power except for starting the starter, 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. At the same time, maintenance-free property that suppresses the decrease in the electrolyte due to gas generation during overcharge and eliminates the need for rehydration is required, and the positive electrode substrate alloy has been changed from Pb—Sb system to Pb—Ca system.
しかし近年、自動車は燃費改善や排出ガスの削減が強く求められるようになり、鉛蓄電池の使用条件は大きく変わってきた。その一つは、信号などによる停車中にエンジンを停止するアイドリングストップである。エンジンの停止により発電機からの電力供給も停止するため、この間の車載電装品への電力は鉛蓄電池の放電によって賄うことになる。そのため、従来と比較して深く放電される様になり、鉛蓄電池は深い充放電状態で使用され、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 the usage conditions of lead-acid batteries have changed greatly. One of them is an idling stop that stops the engine while the vehicle is stopped by a signal or the like. Since the power supply from the generator is also stopped when the engine is stopped, the power to the on-vehicle electrical components during this period is covered by the discharge of the lead storage battery. For this reason, the battery is deeply discharged as compared with the conventional case, and the lead-acid battery is used in a deep charge / discharge state, and has a remarkably short life.
この原因の一つは正極基板鉛合金がＰｂ−Ｓｂ系からＰｂ−Ｃａ系に変わったことによるもので、Ｐｂ−Ｓｂ系鉛合金では基板の酸化で生成した５価のＳｂイオンが基板と活物質の界面に強固なα−ＰｂＯ２層を形成し、基板と活物質の密着性を保つとともに高い導電性を確保していた。もう一つの原因は５価のＳｂイオンが活物質に作用してその一部をゲル化し、活物質粒子同士の結合性を強化していると言うものである。そのため、深い充放電を繰り返しても活物質の軟化が抑制されていた。 One of the reasons is that the positive electrode substrate lead alloy is changed from the Pb-Sb system to the Pb-Ca system. In the Pb-Sb system lead alloy, pentavalent Sb ions generated by the oxidation of the substrate are activated with the substrate. A strong α-PbO 2 layer was formed at the interface of the material to maintain the adhesion between the substrate and the active material and ensure high conductivity. Another cause is that pentavalent Sb ions act on the active material to gel a part thereof, thereby strengthening the bonding between the active material particles. Therefore, the softening of the active material was suppressed even after repeated deep charge / discharge.
一方、Ｐｂ−Ｃａ系鉛合金ではＳｂで見られたような作用が弱く、基板と活物質の界面が剥離して電解液である硫酸が侵入して不導体である硫酸鉛を生成し、導電性を著しく損なう結果、早期に寿命に達する現象が現れた。また、放電状態で放置した場合も同様の原因で容量が回復しなくなる現象が現れた。更に、深い充放電を繰り返すとＰｂ−Ｓｂ系鉛合金を用いた場合の半分程度の回数で活物質が軟化し寿命となった。 On the other hand, the Pb—Ca-based lead alloy has a weak effect as seen with Sb, and the interface between the substrate and the active material peels off, and sulfuric acid, which is an electrolytic solution, intrudes to produce lead sulfate, which is a non-conductor. As a result of the significant loss of performance, a phenomenon that reached the end of life has appeared. Further, when left in a discharged state, a phenomenon that the capacity is not recovered due to the same cause appeared. Furthermore, when the deep charge / discharge was repeated, the active material softened and reached the end of life about half the number of times when the Pb—Sb lead alloy was used.
これらの問題を解決するため、正極基板の表面にＳｂを含む層を設ける（特許文献１）、正極活物質にＳｂ化合物を添加する（特許文献２）などして、Ｐｂ-Ｓｂ系鉛合金を用いた場合と同様の効果を得ようとする提案がなされた。 In order to solve these problems, a layer containing Sb is provided on the surface of the positive electrode substrate (Patent Document 1), and an Sb compound is added to the positive electrode active material (Patent Document 2). A proposal was made to obtain the same effect as when used.
一方、自動車などでは自己放電により長期間放電状態で放置される場合があるが、強固な格子−活物質界面を形成してもこの解決には効果がなく、容量の回復が不十分となった。放電放置後の回復性を向上するため、電解液にアルミニウムを添加する方法が提案されている（特許文献３）。 On the other hand, in automobiles and the like, they may be left in a discharged state for a long time due to self-discharge, but even if a strong lattice-active material interface is formed, this solution is not effective and capacity recovery becomes insufficient. . In order to improve the recoverability after leaving the discharge, a method of adding aluminum to the electrolytic solution has been proposed (Patent Document 3).
特許文献１、２記載のように、Ｓｂの添加は一応の成果を収めたが、現在の市場要求を満たすには更なる改良が必要である。また、特許文献３に記載されるように電解液へのアルミニウムの添加は、白残の発生を防止し容量回復性の向上の点では効果は認められたが、軟化抑制等その他の十分な効果は得られなかった。
このような背景の下、格子−活物質界面の不動体化を抑制すると共に活物質の軟化を抑制し、且つ長期放置後の容量回復性を向上する鉛蓄電池を提供することが望まれる。
As described in Patent Documents 1 and 2, the addition of Sb has achieved a certain result, but further improvement is required to meet the current market demand. In addition, as described in Patent Document 3, the addition of aluminum to the electrolytic solution was confirmed to have an effect in terms of preventing the occurrence of white residue and improving capacity recovery, but other sufficient effects such as suppression of softening. Was not obtained.
Under such circumstances, it is desired to provide a lead storage battery that suppresses immobilization of the lattice-active material interface, suppresses softening of the active material, and improves capacity recovery after standing for a long time.
本発明は、鉛−カルシウム系鉛合金から成る正極基板を備える鉛蓄電池において、正極基板表面の少なくとも一部、および／または該正極基板に充填・塗布された正極活物質中にアンチモンおよび砒素を含み、且つ電解液中にアルミニウムイオンを含むことを特徴としたものである。 The present invention provides a lead-acid battery including a positive electrode substrate made of a lead-calcium-based lead alloy, and containing antimony and arsenic in at least a part of the surface of the positive electrode substrate and / or in the positive electrode active material filled and applied to the positive electrode substrate. In addition, the electrolytic solution contains aluminum ions.
本発明は、活物質同士の密着性がアンチモンイオンの作用で強化され、これに砒素イオンを加えることで活物質の導電性が向上し、格子−活物質界面の密着性を高めたのと同じ効果があると考えられる。また、アンチモンのみを活物質に添加したときよりも、砒素を添加することにより水素過電圧の低下を抑えることができ、メンテナンスフリー性を向上させることができる。夫々の添加量は金属換算でアンチモンは正極活物質量の０.００５〜０．５重量％、砒素は０.００５〜１．０重量％とすることが望ましい。 In the present invention, the adhesion between the active materials is enhanced by the action of antimony ions, and by adding arsenic ions to this, the conductivity of the active material is improved and the adhesion at the lattice-active material interface is increased. It is considered effective. In addition, a decrease in hydrogen overvoltage can be suppressed by adding arsenic than when only antimony is added to the active material, and maintenance-free property can be improved. It is desirable that the respective addition amounts be 0.005 to 0.5% by weight of antimony in the amount of positive electrode active material and 0.005 to 1.0% by weight of arsenic in terms of metal.
次に、アルミニウムイオンの効果は、放電放置における電解液中の硫酸イオン濃度の低下を抑制することにとどまらず、正極及び負極に生成する硫酸鉛の結晶の粗大化や緻密化を抑制して、回復充電時の充電受け入れ性を大幅に改善する効果がある。添加量は、電解液に対して硫酸塩換算で２〜５０ｇ／ｌの範囲が適当である。２ｇ／ｌ未満では効果が不十分であり、５０ｇ／ｌを越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。アンチモンや砒素の添加効果により格子界面の導電性を確保し、アルミニウムイオンにより正負極に生成した硫酸鉛の可逆性を高めることが同時に実現されることによって、初めて長期放置後の容量回復性の改善は達成されるものである。そして、正極中のアンチモンと砒素および電解液中へのアルミニウムイオンが相俟って正極活物質の軟化を抑制してサイクル寿命の向上が達成されるものである。 Next, the effect of aluminum ions is not limited to suppressing a decrease in the sulfate ion concentration in the electrolytic solution in the case of leaving the discharge, but suppressing the coarsening and densification of the lead sulfate crystals produced on the positive electrode and the negative electrode, This has the effect of significantly improving the charge acceptance during recovery charging. The addition amount is suitably in the range of 2 to 50 g / l in terms of sulfate with respect to the electrolytic solution. If it is less than 2 g / l, the effect is insufficient, and if it exceeds 50 g / l, the conductivity of the electrolytic solution is lowered and the rapid discharge characteristics at low temperature are lowered. By improving the reversibility of lead sulfate produced on the positive and negative electrodes by aluminum ions at the same time by ensuring the conductivity of the lattice interface by the effect of addition of antimony and arsenic, the capacity recovery after long-term storage is improved for the first time. Is achieved. Then, antimony and arsenic in the positive electrode and aluminum ions in the electrolyte solution are combined to suppress softening of the positive electrode active material, thereby improving the cycle life.
本発明は、格子−活物質界面の不動体化を抑制すると共に活物質の軟化を抑制し、且つ長期放置後の容量回復性を向上することができ、アイドリングストップ、ＨＥＶまたサイクルユースなどの深いＤＯＤの用途での長寿命化が可能で、鉛蓄電池の用途拡大に貢献することができる。 The present invention can suppress the immobilization of the lattice-active material interface, suppress the softening of the active material, and improve the capacity recovery after being left for a long period of time, and has deep idling stop, HEV, cycle use, etc. It can extend the life of DOD applications and contribute to the expansion of lead storage battery applications.
本発明では、正極基板はカルシウム０．０４重量％、スズ１．０重量％、アルミニウム０．０１５重量％、バリウム０．００８重量％、残部が鉛と不可避の不純物からなる溶融鉛合金をブックモールドによる鋳造によって製造した。この正極基板は、上記に限らずＰｂ−Ｃａ−Ａｌ、Ｐｂ−Ｃａ−Ｓｎ−Ａｌ等のＰｂ−Ｃａ系鉛合金なら何であっても良い。 In the present invention, the positive electrode substrate is made of 0.04% by weight calcium, 1.0% by weight tin, 0.015% by weight aluminum, 0.008% by weight barium, and the remainder is a molten lead alloy consisting of lead and inevitable impurities. Manufactured by casting. The positive electrode substrate is not limited to the above, and may be any Pb—Ca-based lead alloy such as Pb—Ca—Al, Pb—Ca—Sn—Al.
次に、正極用鉛粉に酸化アンチモン及び三酸化二砒素を加えて混合した。これらの添加量は表１に記載の通り種々変化させた。この混合鉛粉を用いて公知の方法で調製した正極ペーストを上記正極基板に充填し、熟成し、乾燥して正極未化成板を得た。これを公知の方法で製造した負極未化成板とポリエチレンセパレータを組み合わせ、硫酸アルミニウムを添加した希硫酸水溶液からなる電解液を注入して電槽化成を行い、５時間率容量が５０ＡｈのＤ２３サイズの１２Ｖ鉛蓄電池を各々試作した。 Next, antimony oxide and diarsenic trioxide were added to and mixed with the lead powder for the positive electrode. These addition amounts were variously changed as shown in Table 1. A positive electrode paste prepared by a known method using this mixed lead powder was filled in the positive electrode substrate, aged, and dried to obtain a positive electrode unformed plate. This was combined with a negative electrode unformed plate produced by a known method and a polyethylene separator, and an electrolytic solution consisting of a dilute sulfuric acid aqueous solution added with aluminum sulfate was injected to form a battery case, and the D23 size of 5 hours rate capacity was 50 Ah. Each 12V lead acid battery was prototyped.
また、硫酸アルミニウムの電解液への添加量は表１に記載の通り種々変化させた。この鉛蓄電池を用いてＪＩＳＤ５３０１に記載される重負荷寿命の試験方法により、寿命を評価した。これとは別に、放電放置試験を行った。即ち、鉛蓄電池を６Ｖになるまで完全放電し、６０℃の環境下に４週間放置後の容量回復性を常温で鉛蓄電池を１５Ｖになるまで充電した後の０.２Ｃで放電した時の放電容量を初期容量と比較することにより評価した。 Further, the amount of aluminum sulfate added to the electrolytic solution was variously changed as described in Table 1. Using this lead storage battery, the life was evaluated by the heavy load life test method described in JIS D5301. Separately from this, a discharge standing test was conducted. That is, the lead storage battery is completely discharged until 6V, and the capacity recovery after leaving for 4 weeks in an environment of 60 ° C is discharged at 0.2C after charging the lead storage battery to 15V at room temperature. The capacity was evaluated by comparing with the initial capacity.
その結果を表１に示した。表１においてアンチモンと砒素の量は、正極活物質に対する金属換算した重量％である。本発明の鉛蓄電池（本発明１〜９）はサイクル寿命回数が多く長寿命であるとともに、容量回復性も優れていることがわかる。これに対し、正極ペースト中にアンチモンや砒素を含まず、且つ、電解液中にアルミニウムを添加しないもの（比較例１）や、正極ペースト中にアンチモンや砒素を添加したのみのもの（比較例２、３）や、電解液中にアルミニウムを添加したのみのもの（比較例４）はサイクル寿命、容量回復性共に低い値となっている。 The results are shown in Table 1. In Table 1, the amounts of antimony and arsenic are weight percentages in terms of metal based on the positive electrode active material. It can be seen that the lead storage battery of the present invention (present inventions 1 to 9) has a long cycle life and a high capacity recovery property. In contrast, the positive electrode paste does not contain antimony or arsenic, and the electrolyte does not contain aluminum (Comparative Example 1), or the positive electrode paste contains only antimony or arsenic (Comparative Example 2). 3) and those in which only aluminum is added to the electrolytic solution (Comparative Example 4) have low values in both cycle life and capacity recovery.
本発明１〜６の鉛蓄電池はアルミニウムの電解液中への添加量を２０ｇ／ｌと一定とし、アンチモンおよび砒素の正極への添加量を種々変化させたものである。アンチモンおよび砒素を正極へ添加することによりサイクル寿命が改善され、さらに電解液中へアルミニウムを添加することで相乗効果を生み、容量回復性の改善も行える。なお、本発明６の鉛蓄電池はアンチモンおよび砒素の添加量が多いため、サイクル寿命および容量回復性は低下する傾向にあり、添加量はアンチモンが金属換算で正極活物質に対して０.００５〜０.５重量％、また砒素は０.００５〜１.０重量％が好ましい。 In the lead acid batteries of the present invention 1 to 6, the amount of aluminum added to the electrolyte is kept constant at 20 g / l, and the amounts of antimony and arsenic added to the positive electrode are variously changed. By adding antimony and arsenic to the positive electrode, the cycle life can be improved, and by adding aluminum to the electrolyte, a synergistic effect can be obtained and capacity recovery can be improved. In addition, since the lead storage battery of the present invention 6 has a large amount of addition of antimony and arsenic, the cycle life and capacity recoverability tend to decrease, and the amount of addition is 0.005 to 0.005% of the positive electrode active material in terms of metal conversion. 0.5 wt% is preferable, and arsenic is preferably 0.005 to 1.0 wt%.
また、本発明４、７〜９の鉛蓄電池はアンチモンおよび砒素の正極への添加量を一定とし、アルミニウムの電解液中への添加量を種々変化させたものである。アルミニウムの電解液中への添加量を増加することにより容量回復性は改善されるが、５０ｇ／ｌを超えると性能は低下する傾向があり２〜５０ｇ／ｌが好ましい。 In addition, the lead storage batteries of the present inventions 4 and 7 to 9 are obtained by making the addition amount of antimony and arsenic to the positive electrode constant and changing the addition amount of aluminum into the electrolytic solution in various ways. The capacity recovery is improved by increasing the amount of aluminum added to the electrolyte, but if it exceeds 50 g / l, the performance tends to decrease, and 2 to 50 g / l is preferred.
尚、本発明は連続鋳造、圧延加工などの方法による基板にも適用することができる。また、本実施例ではアンチモンや砒素は酸化物、並びにアルミニウムは硫酸塩として添加したが、硫酸水溶液や水に可溶性であれば混合し易く、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化合物として添加することができる。砒素は硫化砒素、金属砒素でも良い。また、アンチモンは３価又は５価の何れの化合物でも同様の効果が得られる。 In addition, this invention is applicable also to the board | substrate by methods, such as continuous casting and rolling. In this example, antimony and arsenic were added as oxides, and aluminum was added as sulfates. However, if they are soluble in sulfuric acid aqueous solution or water, they are easy to mix, carbonates, bicarbonates, phosphates, borates. It can be added as a compound such as hydroxide or aluminate. Arsenic may be arsenic sulfide or metal arsenic. Moreover, the same effect is acquired even if antimony is trivalent or pentavalent compound.
更に、正極基板をアンチモンと砒素の溶液に浸漬してその表面にアンチモンおよび砒素を含む層を形成した場合も同様の効果が得られた。また、アンチモンおよび砒素を正極基板および活物質の両方へ付与しても良いことは勿論である。
Further, the same effect was obtained when the positive electrode substrate was immersed in an antimony and arsenic solution to form a layer containing antimony and arsenic on the surface. Of course, antimony and arsenic may be applied to both the positive electrode substrate and the active material.
Claims (1)
A lead-acid battery including a positive electrode substrate made of a lead-calcium-based lead alloy, and containing at least a part of the positive electrode substrate surface and / or a positive electrode active material filled and applied to the positive electrode substrate, and containing antimony and arsenic Lead-acid battery containing aluminum ions inside.
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| JP2008243606A (en) * | 2007-03-27 | 2008-10-09 | Furukawa Battery Co Ltd:The | Lead acid storage battery |
| WO2009142220A1 (en) * | 2008-05-20 | 2009-11-26 | 株式会社ジーエス・ユアサコーポレーション | Lead storage battery and process for producing the lead storage battery |
| WO2015163287A1 (en) * | 2014-04-22 | 2015-10-29 | 日立化成株式会社 | Bisphenol resin, electrode, and lead-acid battery |
| JP2018198151A (en) * | 2017-05-24 | 2018-12-13 | 古河電池株式会社 | Lead storage battery |
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| JP2008243606A (en) * | 2007-03-27 | 2008-10-09 | Furukawa Battery Co Ltd:The | Lead acid storage battery |
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| WO2015163287A1 (en) * | 2014-04-22 | 2015-10-29 | 日立化成株式会社 | Bisphenol resin, electrode, and lead-acid battery |
| JPWO2015163287A1 (en) * | 2014-04-22 | 2017-04-13 | 日立化成株式会社 | Bisphenol resin, electrode and lead acid battery |
| JP2018198151A (en) * | 2017-05-24 | 2018-12-13 | 古河電池株式会社 | Lead storage battery |
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