JP2013134957A - Method for manufacturing lead-acid battery, and lead-acid battery - Google Patents
Method for manufacturing lead-acid battery, and lead-acid battery Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 41
- -1 aluminum ions Chemical class 0.000 claims abstract description 39
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 35
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 33
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 20
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 239000008151 electrolyte solution Substances 0.000 claims description 31
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 32
- 229910021645 metal ion Inorganic materials 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 7
- 230000019635 sulfation Effects 0.000 description 7
- 238000005670 sulfation reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910001414 potassium ion Inorganic materials 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229910014474 Ca-Sn Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 231100000989 no adverse effect Toxicity 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 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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- 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
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Abstract
Description
この発明は鉛蓄電池の製造方法と製造された鉛蓄電池とに関し、特に電解液への金属イオンの添加に関する。 The present invention relates to a method of manufacturing a lead storage battery and a manufactured lead storage battery, and more particularly to the addition of metal ions to an electrolytic solution.
鉛蓄電池の電解液にナトリウムイオン，リチウムイオン，アルミニウムイオン，マグネシウムイオン等を含有させることが行われている。例えばこれらのイオンは正極板と負極板間の短絡の防止に有効であり、またアルミニウムイオンはサルフェーションの防止に有効であることが知られている（特許文献１：特開2008-243606）。そして正極板と負極板とを電槽化成する場合、これらのイオンを電槽化成前の電解液に添加することが常識として行われている。例えば特許文献１では、アルミニウムイオンを添加済みの電解液を注入し、次いで電槽化成するとしている。 Sodium ion, lithium ion, aluminum ion, magnesium ion, etc. are included in the electrolyte solution of a lead storage battery. For example, it is known that these ions are effective in preventing a short circuit between the positive electrode plate and the negative electrode plate, and aluminum ions are effective in preventing sulfation (Patent Document 1: JP 2008-243606). And when forming a positive electrode plate and a negative electrode plate into a battery case, it is common knowledge to add these ions to the electrolyte before battery case formation. For example, in Patent Document 1, an electrolytic solution to which aluminum ions have been added is injected, and then a battery case is formed.
これとは別に発明者の属する研究グループは、電解液に各0.02mol/L以上で0.2mol/L以下のリチウムイオンとアルミニウムイオンとを含有させると、活物質のサルフェーションが少なく、かつ低温高率放電性能に優れた鉛蓄電池が得られることを見出した（特許文献２：特願2010-220913）。発明者らの研究グループでは、電槽化成前に限らず、電槽化成後にリチウムイオン，アルミニウムイオンを添加することも可能であることを認識していた（特許文献２）。そして発明者はその後にリチウムイオン，アルミニウムイオン等の添加時期の影響を調査し、この発明に到った。 Apart from this, the research group to which the inventor belongs has less sulfation of the active material and low temperature and high rate when the electrolyte contains 0.02 mol / L or more and 0.2 mol / L or less of lithium ions and aluminum ions. It was found that a lead storage battery having excellent discharge performance can be obtained (Patent Document 2: Japanese Patent Application No. 2010-220913). The inventors' research group recognized that lithium ions and aluminum ions can be added not only before battery case formation but also after battery case formation (Patent Document 2). The inventor then investigated the influence of the addition timing of lithium ions, aluminum ions, etc., and reached the present invention.
この発明の課題は、鉛蓄電池の充電受入性を改善することにある。 The subject of this invention is improving the charge acceptance of a lead acid battery.
この発明は、正極板と負極板と電解液とを電槽に保持させて、電槽化成により正極板と負極板とを化成する鉛蓄電池の製造方法であって、
前記電解液のナトリウムイオン，リチウムイオン，アルミニウムイオン，及びマグネシウムイオンの濃度がそれぞれ0.02mol/L未満の状態で電槽化成を行い、
電槽化成後に、前記電解液にナトリウムイオン，リチウムイオン，アルミニウムイオン，マグネシウムイオンのいずれかのイオンを0.02mol/L以上0.2mol/L以下の濃度で添加することを特徴とする。
The present invention is a method for producing a lead storage battery in which a positive electrode plate, a negative electrode plate, and an electrolytic solution are held in a battery case, and the positive electrode plate and the negative electrode plate are formed by battery case formation,
In the state where the concentration of sodium ion, lithium ion, aluminum ion, and magnesium ion in the electrolyte solution is less than 0.02 mol / L, respectively,
After the formation of the battery case, any one of sodium ion, lithium ion, aluminum ion and magnesium ion is added to the electrolytic solution at a concentration of 0.02 mol / L or more and 0.2 mol / L or less.
発明者は、電槽化成後にナトリウムイオン等を電解液に添加すると、最初からナトリウムイオン等を含む状態で電槽化成する場合よりも、鉛蓄電池の充電受入性が向上することを見出した。なお電槽化成時のナトリウムイオン等の濃度は0.02mol/L未満、好ましくは0.01mol/L以下であればよい。この効果はナトリウムイオン，リチウムイオン，アルミニウムイオン，マグネシウムイオンに対して生じ、カリウムイオンでは効果が小さかった。充電受入性の改善は、電槽化成後に添加するイオンの濃度が0.02mol/L以上で生じ、0.2mol/Lを越えると効果が小さくなる（表１）。電槽化成前に電解液がナトリウムイオン，リチウムイオン，アルミニウムイオン，マグネシウムイオンを含んでいても、それらの濃度がそれぞれ0.02mol/L未満、特に0.01mol/L以下では充電受入性への悪影響は小さい（表２）。 The inventor has found that when a sodium ion or the like is added to the electrolytic solution after the formation of the battery case, the charge acceptability of the lead storage battery is improved as compared with the case where the battery case is formed in a state containing sodium ions or the like from the beginning. It should be noted that the concentration of sodium ions and the like during the formation of the battery case is less than 0.02 mol / L, preferably 0.01 mol / L or less. This effect was produced for sodium ions, lithium ions, aluminum ions, and magnesium ions, while potassium ions were less effective. The improvement in charge acceptance occurs when the concentration of ions added after the formation of the battery case is 0.02 mol / L or more, and the effect is reduced when it exceeds 0.2 mol / L (Table 1). Even if the electrolyte contains sodium ion, lithium ion, aluminum ion, and magnesium ion before the formation of the battery case, if the concentration is less than 0.02 mol / L, especially 0.01 mol / L or less, there is no adverse effect on charge acceptance. Small (Table 2).
充電受入性では、ナトリウムイオン，リチウムイオン，アルミニウムイオン，マグネシウムイオンの合計濃度ではなく、それぞれのイオン単独の濃度が問題となる。例えばリチウムイオンとアルミニウムイオンとを各0.2mol/L添加すると、リチウムイオンのみを0.2mol/L添加した場合、及びアルミニウムイオンのみを0.2mol/L添加した場合とほぼ同等の効果が得られる（表１）。さらに充電受入性の改善は一時的な現象ではなく、鉛蓄電池の寿命近くまで続く現象である。なおナトリウムイオン，リチウムイオン，アルミニウムイオン，マグネシウムイオンを、電槽化成後に電解液に添加しても、電槽化成前に添加しても、鉛蓄電池の容量、低温高率放電性能等の他の性能は変わらない。この発明はナトリウムイオン等の添加時期を変えるだけで実施でき、しかも弊害即ち背反事象がない。 In charge acceptance, the concentration of each ion alone becomes a problem, not the total concentration of sodium ions, lithium ions, aluminum ions, and magnesium ions. For example, when 0.2 mol / L of lithium ions and aluminum ions are added, the same effect is obtained as when 0.2 mol / L of only lithium ions is added and 0.2 mol / L of only aluminum ions are added (Table 1). 1). Furthermore, the improvement in charge acceptance is not a temporary phenomenon, but a phenomenon that continues until the life of the lead-acid battery. In addition, sodium ion, lithium ion, aluminum ion, magnesium ion can be added to the electrolyte after the battery is formed, or added before the battery is formed. Performance does not change. The present invention can be carried out only by changing the timing of addition of sodium ions and the like, and there is no adverse effect or contradiction.
好ましくは、電槽化成後に電解液にアルミニウムイオンを添加する。特に好ましくは、電槽化成後に電解液にリチウムイオン及びアルミニウムイオンを添加する。好ましくは、鉛蓄電池はアイドリングストップ車または充電制御車用の鉛蓄電池である。アルミニウムイオンは鉛蓄電池の充電受入性を改善し、サルフェーションを抑制する効果があることが知られている。そして電槽化成後に電解液にアルミニウムイオンを添加すると、充電受入性を向上し、かつサルフェーションを抑制して寿命性能を向上できる。また発明者の属する研究グループは、電解液中のリチウムイオンは鉛蓄電池の低温高率放電性能を改善することを見出した。そこで電槽化成後に電解液にリチウムイオン及びアルミニウムイオンを添加すると、サルフェーションが少なく、充電受入性と低温高率放電性能とに優れた鉛蓄電池が得られる。このような鉛蓄電池はアイドリングストップ車及び充電制御車に最適で、充電の機会を制限しても高い性能が得られる。なおアイドリングストップ車は停車時にエンジンを停止し鉛蓄電池の電力で電装負荷を動作させる車両を、充電制御車は鉛蓄電池の電圧値に応じてオルタネータを停止または作動させ、鉛蓄電池への充電の機会を制限する車両を意味する。 Preferably, aluminum ions are added to the electrolytic solution after the formation of the battery case. Particularly preferably, lithium ions and aluminum ions are added to the electrolytic solution after the formation of the battery case. Preferably, the lead acid battery is a lead acid battery for an idling stop vehicle or a charge control vehicle. Aluminum ions are known to improve the charge acceptance of lead-acid batteries and to suppress sulfation. When aluminum ions are added to the electrolytic solution after the formation of the battery case, the charge acceptability is improved, and the life performance can be improved by suppressing sulfation. The research group to which the inventors belong also found that lithium ions in the electrolyte improve the low-temperature, high-rate discharge performance of lead-acid batteries. Therefore, when lithium ions and aluminum ions are added to the electrolytic solution after the formation of the battery case, a lead storage battery with less sulfation and excellent charge acceptability and low-temperature high-rate discharge performance can be obtained. Such a lead-acid battery is most suitable for an idling stop vehicle and a charge control vehicle, and high performance can be obtained even if charging opportunities are limited. The idling stop vehicle stops the engine when it is stopped and operates the electrical load with the power of the lead storage battery.The charge control vehicle stops or operates the alternator according to the voltage value of the lead storage battery, and the lead storage battery is charged. Means a vehicle that restricts
また好ましくは、電槽化成後に電解液にナトリウムイオンを0.02mol/L以上0.2mol/L以下の濃度で添加する。ナトリウムイオンは電解液に添加される代表的な金属イオンであり、電槽化成後にナトリウムイオンを添加することにより、充電受入性を改善できる。 Preferably, sodium ions are added to the electrolytic solution at a concentration of 0.02 mol / L or more and 0.2 mol / L or less after the formation of the battery case. Sodium ion is a typical metal ion added to the electrolytic solution, and charge acceptability can be improved by adding sodium ion after the formation of the battery case.
この発明はまた、電槽化成された正極板と、電槽化成された負極板と、電解液とが電槽内に保持されている鉛蓄電池であって、
前記電解液にはナトリウムイオン，リチウムイオン，アルミニウムイオン，マグネシウムイオンのいずれかのイオンが、0.02mol/L以上0.2mol/L以下の濃度で電槽化成後に添加されており、かつ前記電解液の電槽化成前のナトリウムイオン，リチウムイオン，アルミニウムイオン，及びマグネシウムイオンの濃度は、それぞれ0.02mol/L未満であることを特徴とする。好ましくは、電解液にはリチウムイオン及びアルミニウムイオンが電槽化成後に添加されており、鉛蓄電池はかつアイドリングストップ車または充電制御車用の鉛蓄電池である。
The present invention is also a lead storage battery in which a battery case formed positive electrode plate, a battery case formed negative electrode plate, and an electrolytic solution are held in the battery case,
Any one of sodium ion, lithium ion, aluminum ion and magnesium ion is added to the electrolytic solution after the formation of the battery case at a concentration of 0.02 mol / L or more and 0.2 mol / L or less. The concentration of sodium ion, lithium ion, aluminum ion, and magnesium ion before battery case formation is less than 0.02 mol / L, respectively. Preferably, lithium ions and aluminum ions are added to the electrolytic solution after the formation of the battery case, and the lead acid battery is a lead acid battery for an idling stop vehicle or a charge control vehicle.
この明細書で、鉛蓄電池の製造方法に関する記載はそのまま鉛蓄電池にも当てはまる。前記のように電槽化成後にナトリウムイオン，リチウムイオン，アルミニウムイオン，マグネシウムイオンのいずれかのイオンが0.02mol/L以上0.2mol/L以下の濃度で添加された鉛蓄電池は、充電受入性が高いので、充電不足な状態で使用される用途に適している。特に電解液にリチウムイオン及びアルミニウムイオンが電槽化成後に添加された鉛蓄電池は、充電受入性が高く、かつ低温高率放電性能に優れ、さらにサルフェーションが少ないので、アイドリングストップ車及び充電制御車に適している。 In this specification, the description regarding the manufacturing method of a lead acid battery is applied to a lead acid battery as it is. As described above, a lead storage battery in which any one of sodium ion, lithium ion, aluminum ion, and magnesium ion is added at a concentration of 0.02 mol / L or more and 0.2 mol / L or less after the formation of the battery case has high charge acceptability. Therefore, it is suitable for applications used in a state where charging is insufficient. In particular, lead-acid batteries in which lithium ions and aluminum ions are added to the electrolyte after the formation of the battery case have high charge acceptability, excellent low-temperature, high-rate discharge performance, and low sulfation. Is suitable.
以下に、本願発明の最適実施例を示す。本願発明の実施に際しては、当業者の常識及び先行技術の開示に従い、実施例を適宜に変更できる。 Hereinafter, an optimum embodiment of the present invention will be described. In carrying out the present invention, the embodiments can be appropriately changed in accordance with common sense of those skilled in the art and disclosure of prior art.
ボールミル法で製造した鉛粉にカーボンブラックと合成樹脂繊維とBaSO4とリグニンとを水と硫酸とで混練し、負極活物質ペーストとした。同様にボールミル法で製造した鉛粉に合成樹脂繊維を水と硫酸とで混練し、正極活物質ペーストとした。添加物の含有量は、負極活物質ペーストの場合、ボールミル法で製造した鉛粉100mass%に対して、カーボンブラックが0.3mass%、合成樹脂繊維が0.1mass%、BaSO4 0.6mass%、リグニンは0.2mass%であった。また正極活物質ペーストの場合、ボールミル法で製造した鉛粉100mass%に対して合成樹脂繊維が0.1mass%であった。鉛粉はバートン法等で製造しても良く、鉛粉中の鉛丹含有率等は任意で、ペーストへの添加物は任意である。また電槽化成時にリグニンからナトリウムイオンは電解液へ溶け出すが、リグニン由来のナトリウムイオンの濃度は一般に0.01mol/L未満である。 Carbon black, synthetic resin fiber, BaSO 4 and lignin were kneaded with water and sulfuric acid to lead powder produced by the ball mill method to obtain a negative electrode active material paste. Similarly, a synthetic resin fiber was kneaded with water and sulfuric acid to lead powder produced by a ball mill method to obtain a positive electrode active material paste. The content of additives in the case of the negative electrode active material paste for lead powder 100 mass% was prepared by ball milling the carbon black is not more than 0.3 mass%, the synthetic resin fibers 0.1mass%, BaSO 4 0.6mass%, lignin It was 0.2 mass%. In the case of the positive electrode active material paste, the synthetic resin fiber was 0.1 mass% with respect to 100 mass% of the lead powder produced by the ball mill method. Lead powder may be manufactured by the Burton method, etc. The lead content in the lead powder is arbitrary, and the additive to the paste is arbitrary. In addition, sodium ions are dissolved from the lignin into the electrolyte during the formation of the battery case, but the concentration of sodium ions derived from the lignin is generally less than 0.01 mol / L.
負極活物質ペーストをPb-Ca-Sn系合金から成る負極格子へ充填し、正極活物質ペーストを同様にPb-Ca-Sn系合金から成る正極格子へ充填し、各々50℃相対湿度50％で48時間の熟成と、次いで50℃の乾燥雰囲気で24時間の乾燥とを施し、未化成の負極板と未化成の正極板とした。未化成の負極板を微細な気孔を有する袋状のポリエチレンセパレータに収納し、負極板８枚と正極板７枚とを交互に積層して、未化成の極板群とした。未化成の極板群を６個直列に電槽に収納し、20℃で比重が1.230の硫酸を電槽内に注いで、正極活物質理論容量の220%の電気量を通電することにより電槽化成を行い、液式鉛蓄電池とした。なお液式ではなく、制御弁式鉛蓄電池としても良く、セパレータの種類、電槽化成時の通電量等は任意である。 The negative electrode active material paste was filled into the negative electrode lattice made of Pb-Ca-Sn alloy, and the positive electrode active material paste was similarly filled into the positive electrode lattice made of Pb-Ca-Sn alloy, each at 50 ° C and 50% relative humidity. Aging was carried out for 48 hours, followed by drying in a dry atmosphere at 50 ° C. for 24 hours to obtain an unformed negative electrode plate and an unformed positive electrode plate. The unformed negative electrode plate was accommodated in a bag-like polyethylene separator having fine pores, and 8 negative electrode plates and 7 positive electrode plates were alternately laminated to form an unformed electrode plate group. Six unformed electrode plate groups are housed in series in a battery case, sulfuric acid having a specific gravity of 1.230 at 20 ° C is poured into the battery case, and electricity is supplied by applying an electric quantity of 220% of the theoretical capacity of the positive electrode active material. The tank was formed into a liquid lead-acid battery. In addition, it is good also as a control valve type lead acid battery instead of a liquid type, and the kind of separator, the energization amount at the time of battery case formation, etc. are arbitrary.
電解液に添加する金属イオンとして、ナトリウムイオン，リチウムイオン，カリウムイオン，アルミニウムイオン，マグネシウムイオンを選び、化成後の電解液での濃度が0〜0.3mol/Lとなる範囲で変更した。電槽化成後にこれらの金属イオンを添加することを「後添加」と呼び、電槽化成に用いた硫酸中に含有させておくことを「前添加」と呼ぶ。そしてこれらのイオン全量を後添加もしくは前添加したものと、一部を前添加し残りを後添加したものとを製造した。 Sodium ions, lithium ions, potassium ions, aluminum ions, and magnesium ions were selected as metal ions to be added to the electrolytic solution, and the concentration was changed within a range of 0 to 0.3 mol / L after the chemical conversion. Adding these metal ions after the formation of the battery case is called “post-addition”, and adding it in the sulfuric acid used for forming the battery case is called “pre-addition”. And what added these ion whole quantity after addition or pre-addition, and what added a part and pre-added the remainder were manufactured.
後添加では、電槽化成後の電解液の液面が一定の高さとなるように、電解液を抽出もしくは追加することにより液面の高さを調整した。次いで所定濃度の金属イオンを含む硫酸を所定容積ずつ追加することにより、一定量の電解液を有する鉛蓄電池とした。金属イオンが電解液中で均一に分布するように、金属イオンは硫酸に溶解した状態で添加することが好ましい。実施例では、ナトリウムイオン，カリウムイオン，アルミニウムイオン，マグネシウムイオンは硫酸塩を硫酸と混合し、リチウムイオンは炭酸塩を硫酸と混合した。なお硫酸とNa2SO4等の固体の金属塩を別々に電解液に加え、補充電により電極から酸素、水素等のガスを発生させることにより、ナトリウムイオン等のイオンを電解液中に拡散させても良い。 In the post-addition, the height of the liquid level was adjusted by extracting or adding the electrolytic solution so that the level of the electrolytic solution after the formation of the battery case was a constant height. Subsequently, a lead acid battery having a certain amount of electrolyte was obtained by adding sulfuric acid containing metal ions of a predetermined concentration by a predetermined volume. It is preferable to add the metal ion in a state dissolved in sulfuric acid so that the metal ion is uniformly distributed in the electrolytic solution. In the examples, sodium ions, potassium ions, aluminum ions, and magnesium ions were mixed with sulfate and sulfuric acid, and lithium ions were mixed with carbonate and sulfuric acid. In addition, solid metal salts such as sulfuric acid and Na 2 SO 4 are separately added to the electrolyte, and oxygen, hydrogen, and other gases are generated from the electrode by supplementary charging, thereby diffusing ions such as sodium ions into the electrolyte. May be.
電槽化成時の硫酸濃度を完成した鉛蓄電池での濃度よりも低くし、電槽化成後に電解液を一部取り出して、金属イオンを予め溶解した高濃度の硫酸を注いでも良い。この場合、高濃度の硫酸を注入することにより、金属イオンの添加と硫酸濃度の調整とを行う。なお高濃度の硫酸を追加する前に電解液の液面を一定高さに調整しても、高濃度の硫酸を追加した後に電解液の液面を調整しても良い。また金属イオンの効果の差は、後添加か前添加かにより生じ、化成時の硫酸濃度の差により生じるのではない。 The sulfuric acid concentration at the time of battery case formation may be made lower than the concentration of the completed lead storage battery, a part of the electrolytic solution may be taken out after the battery case formation, and high concentration sulfuric acid in which metal ions are dissolved in advance may be poured. In this case, metal ions are added and the sulfuric acid concentration is adjusted by injecting high concentration sulfuric acid. The liquid level of the electrolytic solution may be adjusted to a certain level before adding high concentration sulfuric acid, or the liquid level of the electrolytic solution may be adjusted after adding high concentration sulfuric acid. The difference in the effect of metal ions is caused by post-addition or pre-addition, not by the difference in sulfuric acid concentration during chemical conversion.
電解液中の金属イオンの濃度と添加時期とが同じ鉛蓄電池を３個ずつ用い、JIS D 5301規定の充電受入性、5時間率容量、低温高率放電特性及び、SBA S 0101規定のアイドリングストップ寿命を測定した。結果を３個の蓄電池の平均値で表１，表２に示す。 Three lead-acid batteries with the same metal ion concentration and addition time in the electrolyte are used, charge acceptance as defined in JIS D 5301, 5-hour rate capacity, low-temperature high-rate discharge characteristics, and idling stop as defined in SBA S 0101 Lifespan was measured. The results are shown in Tables 1 and 2 as average values of three storage batteries.
表１及び後述の表２は５時間率電流で0.5時間放電した後、12時間室温で放置し、14.4Vの定電圧で10秒間充電した際の電気量を示し、充電電流は最大100Aに制限し、周囲温度は25℃であった。電解液中の金属イオンの濃度を0.01mol/Lから0.3mol/Lの範囲で変化させた際の結果を表１に示し、全量を前添加した場合を100%として、全量を後添加した際の結果を示す。ナトリウムイオン、アルミニウムイオン、リチウムイオン、マグネシウムイオンを添加する場合では、後添加の方が前添加よりも鉛蓄電池が受け入れた充電電気量が大きい。充電受入性の差は前添加か後添加で定まり、言い換えると金属イオンを電槽化成前に添加するか後で添加するかにより生じる。また、添加時期の影響は各イオンの濃度が0.02mol/L以上0.2mol/L以下で大きく、0.01mol/Lと0.3mol/Lとでは小さい。一方、カリウムイオンの場合では、添加時期による充電受入性の差は僅かになった。 Table 1 and Table 2 below show the amount of electricity when discharged for 5 hours at a current of 0.5 hours, left at room temperature for 12 hours, and charged for 10 seconds at a constant voltage of 14.4 V. The charging current is limited to a maximum of 100 A. The ambient temperature was 25 ° C. Table 1 shows the results when the concentration of metal ions in the electrolyte was changed in the range of 0.01 mol / L to 0.3 mol / L. When the total amount was pre-added, the total amount was 100%. The results are shown. In the case of adding sodium ion, aluminum ion, lithium ion, and magnesium ion, the post-addition has a larger amount of charge electricity accepted by the lead storage battery than the pre-addition. The difference in charge acceptability is determined by pre-addition or post-addition, in other words, depending on whether the metal ions are added before or after the formation of the battery case. The influence of the addition time is large when the concentration of each ion is 0.02 mol / L or more and 0.2 mol / L or less, and is small between 0.01 mol / L and 0.3 mol / L. On the other hand, in the case of potassium ion, the difference in charge acceptability depending on the addition time became small.
金属イオンの全量を後添加した場合と、金属イオン中の0.01mol/L分を前添加し残りを後添加した場合の結果を表２に示し、測定条件は表1と同じである。金属イオンを0.01mol/L前添加しても結果は同じである。 Table 2 shows the results when the total amount of metal ions was added later and when 0.01 mol / L in metal ions was added in advance and the remainder was added later. The measurement conditions are the same as in Table 1. The result is the same even if metal ions are added in an amount of 0.01 mol / L.
金属イオンを前添加するか後添加するかは、容量、低温高率放電性能には影響しないことが分かった。金属イオンを後添加すると、充電受入性が増すため、アイドリングストップ寿命が前添加の場合よりも向上した。また0.02mol/L以上0.2mol/L以下のアルミニウムイオンと0.02mol/L以上0.2mol/L以下のリチウムイオンとを共に含む電解液を用いると、低温高率放電性能に優れ、サルフェーションが少ないためアイドリングストップ車に適した鉛蓄電池が得られることを、発明者の属する研究グループは確認済みである（特許文献２）。 It was found that whether the metal ions were added before or after did not affect the capacity and the low-temperature high-rate discharge performance. When metal ions are added later, the charge acceptability is increased, so that the idling stop life is improved as compared with the case of prior addition. Also, when using an electrolyte containing both 0.02 mol / L to 0.2 mol / L lithium ions and 0.02 mol / L to 0.2 mol / L lithium ions, it has excellent low-temperature high-rate discharge performance and low sulfation. The research group to which the inventor belongs has been confirmed that a lead storage battery suitable for an idling stop vehicle can be obtained (Patent Document 2).
以上のように実施例では、
・ 充電受入性に優れた鉛蓄電池が得られ、
・ この効果は電槽化成後にナトリウムイオン，リチウムイオン，アルミニウムイオン，マグネシウムイオンのいずれかのイオンを0.02mol/L以上0.2mol/L以下の濃度で添加する場合に著しく、
・ ナトリウムイオン等に代えて、カリウムイオンを電槽化成後に添加しても効果は小さい。
・ またリチウムイオンとアルミニウムイオンとを電槽化成後に電解液に添加すると、アイドリングストップ車、充電制御車に最適な鉛蓄電池が得られ、
・ ナトリウムイオンの場合でも、電槽化成後に添加することにより、充電受入性を改善できる。
As described above, in the embodiment,
・ Lead-acid batteries with excellent charge acceptance can be obtained,
・ This effect is remarkable when sodium ion, lithium ion, aluminum ion, or magnesium ion is added at a concentration of 0.02 mol / L or more and 0.2 mol / L or less after the battery is formed.
-Even if potassium ions are added after the formation of the battery case instead of sodium ions, the effect is small.
・ In addition, when lithium ions and aluminum ions are added to the electrolyte after the formation of the battery case, an optimum lead storage battery for idling stop vehicles and charge control vehicles can be obtained.
-Even in the case of sodium ion, the charge acceptability can be improved by adding it after the formation of the battery case.
Claims (7)
前記電解液のナトリウムイオン，リチウムイオン，アルミニウムイオン，及びマグネシウムイオンの濃度がそれぞれ0.02mol/L未満の状態で電槽化成を行い、
電槽化成後に、前記電解液にナトリウムイオン，リチウムイオン，アルミニウムイオン，マグネシウムイオンのいずれかのイオンを0.02mol/L以上0.2mol/L以下の濃度で添加することを特徴とする鉛蓄電池の製造方法。 A method for producing a lead storage battery in which a positive electrode plate, a negative electrode plate, and an electrolytic solution are held in a battery case, and a positive electrode plate and a negative electrode plate are formed by battery case formation,
In the state where the concentration of sodium ion, lithium ion, aluminum ion, and magnesium ion in the electrolyte solution is less than 0.02 mol / L, respectively,
A lead-acid battery manufacturing method comprising adding sodium ion, lithium ion, aluminum ion, or magnesium ion to the electrolyte at a concentration of 0.02 mol / L or more and 0.2 mol / L or less after the formation of the battery case Method.
前記電解液にはナトリウムイオン，リチウムイオン，アルミニウムイオン，マグネシウムイオンのいずれかのイオンが、0.02mol/L以上0.2mol/L以下の濃度で電槽化成後に添加されており、かつ前記電解液の電槽化成前のナトリウムイオン，リチウムイオン，アルミニウムイオン，及びマグネシウムイオンの濃度は、それぞれ0.02mol/L未満であることを特徴とする鉛蓄電池。 A lead-acid battery in which a positive electrode plate formed in a battery case, a negative electrode plate formed in a battery case, and an electrolytic solution are held in the battery case,
Any one of sodium ion, lithium ion, aluminum ion and magnesium ion is added to the electrolytic solution after the formation of the battery case at a concentration of 0.02 mol / L or more and 0.2 mol / L or less. Lead acid battery characterized in that the concentration of sodium ion, lithium ion, aluminum ion and magnesium ion before battery case formation is less than 0.02 mol / L, respectively.
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